INTERNALLY CHARGED HYDROPHOBICALLY MODIFIED COPOLYMERS

COPOLYMERES MODIFIES DE FACON HYDROPHOBIQUE ET CHARGES DE FACON INTERNE

English Abstract

ABSTRACT OF THE DISCLOSURE
Polymers of the structure
<IMG> (I)
(W) (X) (Y) (Z)
and
<IMG> (II)
(A) (B)

wherein G is -OH and OR3SO3-M+;
Q is -OR3-; -NHR3 ; -OR3MHCONHR3-, and
-OR3NHCOOR3-;
R is H or methyl;
R1 is an alkyl of from 1 to 4 carbons, especially
methyl;
R2 is an alkyl of from 10 to 24 carbons, preferably
from 12 to 18 carbons
R3 is an alkylene radical of from 2 to 4 carbons,
especially ethyl;
J is an anion especially chloride, bromide or iodide;
M is a cation, especially sodium or potassium;
w, x, y, and z, a and b designate the number of moles
of the monomeric units in accordance with the mole
fraction and mole ratio constraints: w/x and w/y are
about 0.4 or greater; w/z is from about 199:1 to about
0.67:1; w/(x + y + z) is from about 199:1 to about
0.25:1, and a/b is from about 199:1 to about 2.3:1, w,
z, a and b being positive, and x and y being less than
or equal to about 0.5, and
m and n are numbers designating the degree of
polymerization.
Also disclosed are compositions and processes employing
the subject polymers in the treatment of hair.
[CP-1067]

Claims

WHAT IS CLAIMED IS:
1. A polymer suitable for the treatment of human hair in
accordance with the following structures:
<IMG> (I)
(W) (X) (Y) (Z)
and
<IMG> (II)
(A) (B)

24
wherein G is -OH and -OR3SO3-M+;
Q is OR3-; -NHR3-; -OR3NHCONHR3-, and
-OR3NHCOOR3-:
R is H or methyl:
R1 is an alkyl of from 1 to 4 carbons;
R2 is an alkyl of from 10 to 24 carbons:
R3 is an alkylene radical of from 2 to 4 carbons;
J is an anion;
M is a cation:
w, x, y, z, a and b designate the number of moles of the
monomeric units in accordance with the mole fraction
and mole ratio constraints: w/x and w/y are about 0.4
or greater: w/z is from about 199:1 to about 0.67:1:
w/(x + y + z) is from about 199:1 to about 0.25:1, and
a/b is from about 199:1 to about 2.3:1, w, z, a and b
being positive, and x and y being less than or
equal to about 0.5, and
m and n designate the degree of polymerization.
2. An aqueous composition useful as hair conditioners
for human hair comprising at least one polymer (I) or (II)
represented by the formulas:

<IMG> (I)
(w) (X) (Y) (Z)
and
<IMG> (II)
(A) (B)
wharein:
G is -OH and -OR3SO3-M+;
Q is -OR3-; -NHR3-; -OR3NHCONHR3-, and
-OR3NHCOOR3-;
R is H or methyl;
R1 is an alkyl of from 1 to 4 carbons;
R2 is an alkyl of from 10 to 24 carbons;
R3 is an alkylene radical of from 2 to 4 carbons;

26
J is an anion;
M is a cation;
w, x, y, z, a and b designate the number of moles of the
monomeric units in accordance with the mole fraction
and mole ratio constraints: w/x and w/y are 0.4 or
greater: w/z is from about 199:1 to about 0.67:1; w/(x
+ y + z ) is from about 199:1 to about 0.25:1, and a/b
is from about 199:1 to about 2.3:1, w, z, a and b
being positive, and x or y being less than or equal to
about 0.5, and
m and n designate the degree of polymerization, and
a cosmetically acceptable aqueous vehicle, the polymer (I) or
(II) being present in the composition in an amount that is
effective when the hair is treated by contact with the
composition for from 1 to 30 minutes to improve combability of
the hair as compared with hair that has not been so treated.
3. A process for conditioning human hair which comprises
contacting the hair with an aqueous composition containing at
least one polymer (I) or (II) represented by the formula-
<IMG> (I)
(W) (X) (Y) (Z)

27
and
<IMG>
(A) ( B)
wherein:
G is -OH and -OR3SO3-M+:
Q is-OR3-: -NHR3-; -OR3NHCONR3 , and
-OR3NHCOOR3 -;
R is H or methyl;
R1 is an alkyl of from 1 to 4 carbons;
R2 is an alkyl of from 10 to 24 carbons:
R3 is an alkylene radical of from 2 to 4 carbons;
J is an anion;
M is a cation;
w, x, y, z, a and b designate the number of moles of the
monomeric units in accordance with the mole fraction and
mole ratio constraints: w/x and w/y are 0.4 or greater:
w/z is from about 199:1 to about 0.67:1; w/(x + y + 2) is
from about: 199:1 to about 0.25:1, and a/b is from about

28
199:1 to about 2.3:1, w, z, a and b being positive
numbers, and x or y being less than or equal to about
0.5, and
m and n designate the degree of polymerization, and
a cosmetically acceptable aqueous vehicle, the polymer (I) or
(II) being present in the composition in an amount that is
effective when the hair is treated by contact with the
composition for from 1 to 30 minutes to improve combability of
the hair, as compared with hair that has not been so treated.
4. The polymer of Claim 1, 2 or 3 wherein the mole
fractions of W, X, Y, Z, A and B are: w from about 0.2 to about
0.995; z from about 0.005 to about 0.3; a from about 0.7 to
about 0.995 and b from about 0.005 to about 0.3.
5. The polymer of Claim 4 wherein the polymer is Polymer
(I).
6. The polymer of Claim 4 wherein the polymer is Polymer
(II).
7. The polymer of Claim 5 wherein the mole fractions of W,
X, Y and Z are: w is from about 0.4 to about 0.95; at lea t one
of x or y is from about 0.1 to about 0.4, and z is from about
0.05 to about 0.2.

29
8. The polymer of Claim 7 wherein the mole ratio
constraints are: w/x from about 9.5:1 to about 1:1, w/y from
about 9.5:1 to about 1:1, w/z from about 19:1 to about 2:1, and
w/(x + y + z) from about 19:1 to about 0.67:1.
9. The polymer of Claim 8 wherein R1 is methyl; R2 is
an alkyl of from 12 to 18 carbons: R3 is ethyl; J is chloride,
bromide or iodide, and M is potassium or sodium.
10. The polymer of Claim 6 wherein the mole
fractions of A and B are: a from about 0.8 to about
0.95 and b from about 0.05 to about 0.2.
11. The polymer of claim 11 wherein the mole
ratio of a/b is from about 19:1 to about 4:1.
12. The polymer of claim 12 wherein R1 is
methyl; R2 is an alkyl of from 12 to 18 carbons,
R3 is ethyl; J is chloride, bromide or iodide, and M
is potassium or sodium.

Description

CP-10~7
INTE~NALLY CHARG~D HYDROPHOBICALLY
MODIFIED COPOLYME~S
-by
Janusz ~achow:icz
and Chittamuru Ramixeddy
The present inv~ntion concerns hydrophobically modified
copolymers for conditioning hair, thQ copolym~rs being
characterized by tha presQnce of internally charged ionic
species. More sp~ci~ically, the invention concerns such
copolymers and compositions containing same for use in
cosmetics, in particular, for use in th~ treat~en~ of hair.
Polym2rs use~ui in preparing hair-trea~ing co~positions are
known in the art. Th~RQ known poly~er~ include homopolymers and
copoly~ers, and may be anionic, cationic, amphoteric or
zwitterionic in character.
.: , . '
- : . .
.

" 'g ~ d
u.S. ~,402,977 to Grollier et al discloses amphoteric
polymers for use in the treatment of keratin fibers, especially
in combination with anionic polymers. U.S. 4,818,245 to
Jachowicz et al discloses certain cationic polymers having a
hydrophobic moiety, the polymers being suitable to reduce static
electricity in the hair. U.S. 4,590,249 to Cabastany et al
discloses cationic ampholytic tetrapolymers useful in treating
hair. U.S. 4,767,616 to Kubota disclo~es hair conditioning
resins prepar2d by modifying a copolymer with a zwitterionic
agent. GB 2,116,689 discloses compositions for conditionin~
:~air ~hich contain at least one anionic polymer and at least one
cationic or a~photeric polymer. GB 1,368,495 discloses hair
setting compositions incorporating copoly~ers including a
zwitterionic monomQr. U.S. 4,65~,848 to SchultZ et al disclos~
certain terpoly~er~ u5Qful as viscosi~iers. U.S. 4,710,555 to
Pfei~fer et al discloses certain tetrapolymers useful as
viscosity enhancers. U.S. 4,730,028 to Bock et al discloses
cationic terpolym~r~ of a zwi~terionic character.
S~m~a~y~of I~vention
The hydrophobic211y modified copolymers of the present
invention incorporate monomeric group3 providing species that
are internally charged. In on~ e~bodimen~ of the in~ention, the
polymers are copolymers, t~rpolymers or tetr~polymers which
comprise (a) a strongly catio~ic hydrophobic mono~er, (b) either

a weakly or a strongly anionic monomer, (c) optionally, a
stron~ly cationic hydrophilic monomer, and (d) optionally, a
weakly cationic monomer.
In another e~bodiment the copolymers of the present inven-
tion comprise (e) a strongly cationic hydrophobic monomer and
(f) a zwitterionic monomer.
The copolymers of the present invention, im view of the
~lural nature o~ th~ir ionic makaupr provide great flexibility
n preparin~ cosmetic for~ulations. Thus, for example, t~e
copolymer~ are sensitive to pH of the cos~etic co~position,
which may be varied, alon~ with the molar ratios of the
monomers, to obtain desirad copolym~r a~tributes.
The pre~erred use for the copolymers of the present inven-
tion lies in the treatment of hair. In particular, in view of
the hydrophobic monomer incorporated within each class of
copolymer set forth abov~, the copolymers of the present
invention are particularly us~ful in the conditioning of hair,
their applic~tion to hair by ms~n~ of a cos~tically acceptable
vehicle enhancing the hair~s ~o~tn~R~, antistatic and tactile
propertie~.
DQtailed Desc2ipt~on of Invention
The two cla~ses of hydrophobically modified copolymers
`
, ~ -
.~ .

2t~ 4
previously referred to may be represented structurally as
~ollows.
H2-cH - - - -cH2-cN _ _ ~CXz-CN- ~ _ CH2 CH _
C o C o C C) C~O ~ I
_~ L ~ N`R,~ R~ J
~w) (X, (Y) (Z)
wherein G is -OH and -OR3SO3 M';
is -OR3-; -NHR3-; -OR3NHCONER3 , and
-OR3NHCOOR3-
R is H or methyl:
Rl i5 an alkyl of from 1 to 4 carbons, e~pecially
methyl;
R2 is an alkyl of from 10 to 24 carbons, pre~erably
from 12 to 18 carbons
R3 is an alkylene radical of from 2 to 4 carbons,
especially ethyl;
J is an anion, especially chloride, bro~ide or iodide: -
M is a cation, e~pecially so~iu~ or potassium;
w, x, y and z are integers designating t~e number of
moles of the ~onomeric units, and --.
: - : . . . , . -
.. : . . .
.-- ,
. .. .. ..

m is a number designating the degree of polymerization.
and
J ~ ~ ~ a II
~ R,~ R~
L _~ L ~ ~ ~
(A) (~
herein R, Rl, R2, R3, Q, J, and M have the dQ~initions
set forth a~ove: a and b are int~rs designating the nu~ber of
moles of t~s monom~ric units, and n is a number designating the
degree of polymerization. (W), (X), (Y), (Z), (A) and (~)
designate speci~ic monomeric groups with the copolymers.
In Polymor I th~ monomers (W) and (Z) are deemed essential
and the mono~Qr (Y) is pr~ferably incorporated, while ~he
monomer (X) is op~i~nal. Monomer (Z), in view of the long chain
alkyl group R2, is hydrophobic, and is also stron~}y cationic
in view of ~he po~ti~ely charged ni~rogen. ~onomer (Y) ls also
strongly cationic, but is hydrophilic by virtue of the short
chain alkyl group~ ~ub~tituted on the qu~ternary nitrogen.
,. . .
. . -
. . .
.

;A. ~ rr~ ~ ~ 6
Monomer (X) is weakly cat~onic, the nitrogen not being
quaternized, and is also hydrophilic.
Monomer (W) may be weakly or strongly anionic, depending
upon the choice of the substitutent group G. Thus, when G is
-OH, the mono~er unit (W) contains a weakly ionizabl~ carboxylic
acid radical. When G is -OR3SO3-M~ he monomer unit
(W) is readily ionized, and (W) is strongly anionic. Both
weakly and strongly anionic monomer units (W) may be present in
the copolymer.
The electrostatic character of the Polymer I is determined
by the molar ratio of anionic to cationic groups, i.e., the
ratio w/(x ~ y + z), and by t~e ~ypa o~ sub~tituent groùp
present in the anionic monomer (W). Th~ ~ore highly ca~ionic
copolymers are prsferred for use as Aair conditionin~ agents,
while the more highly anionic copoly~ers may be employed, as
fur~her disclosed below, in te~porary hair color rinses.
The ratio w/~x ~ y 12) iS genarally within the range of ~rom ~
about 199:1 to abou~ 0.25:1. -:
In Polym~r II ~he monom~rs (A3 and (B~ are bo~h essential~
Mono~er (B), in view o~ the long chain alkyl gr.~up R2 and the
positlvely charged nitro~an, is bot~ cationic and hydrophobic.
The monomsr (A) is zwitterionic. That is, monomer (A) is an
internal salt by virtue of -SO3 M+ group.
.
- - ~ . ::
~: '

The Polymers I and II, becaus~ both positively and nega-
eively charged moieties are pres~nt, may each be reqard~d as
amphoteric, i.e., sensitive to the p~ of the media in which they
are placed, as hereinafter described.
The Polymers I and II may ~e watar-soluble, watar-
dispersible or water~insoluble, depending upon the mole fraction
of the monomers tZ) or (B). Thus, for a water-soluble
copolymer, the mole fraction of monomers (Z) and (B) should be
less than about 0.1, preferably within the range of from about
0.02 to about 0.08. Above a mole fraction of about 0.1
solubilization beco~es difficult, such copolymers being either
water-dispersible or water-insolu~l~. The wat~r-soluble
copolymers are suitable for u~Q in a~ueous cos~etic compositions
without resort to the UsQ of a sur~actant or organic solvent
solubilizer. The water-dispersibl2 and water-insoluble
copolymers may be e~ployed in nonaqueous cos~etic compositions,
or in aqueous co~positions also containing an emulsifying
surfactant or a hydrotrope, or Which incorporate a nonaqueoùs
organic solvent such a~ a Cl to C6 mono- or polyhydric
alcohol, prQferably e~hanol i30propanol, ethylene glycol or
propylene glycol.
The ionic naturo of the Polymers I and II d~pen~s upon the
relati~e proportions of the anionic, cationic or zwitterionic
.. .
~, !

monomeric units, the strength of the ionic charge associated
with a particular monomeric unit, and the pH of the media
containing the copolymer. Thus, a Pol~mer I havinq a high molar
ratio of-strongly cationic monomer units, such as units (Y) and
( Z ), tO weakly anionic monomer units, .such as (W) when G is -OH,
is generally cationic except at high pt~ values. Conversely, a
Polymer I having a low molar ratio of ~strongly cationic monomer
units to ~trongly anionic ~onomer unit~, such as (W) when G
includes SO3 , is generally anionic. For Polymer II, the
_opolymer is typically cationic.
This sensitivity to pH par~its the for~ation of copolymars
that are amphoteric or cationic in acid m~dia and anionic in
basic media, when the ionic str~ngths and molar ratio of the
cationic and anionic monomer units are in balance.
The suitable mole fractions of each of the monomer units are
set forth below.
~AB~
Monomer Uni~ ~ole Fractions
Mo~omer 3road ~ ~~
(W) 0.2-0.995 0.4-0.95
(X) or (Y) o 0.5 0.1-0.4
(Z) 0.005-0.3 0.05-0.2
(A) 0.7-0.995 0.8-0.95
(B) 0.005-O.~ 0.05~0.2

2 ~ , d
The cationic/anionic m~le ratios for the monomer units of
Polymer I are set forth below:
Mole Ratio
Broi~ld Prefer~red
w/x ~0.~:1 9.5:1-1:1
w/y 20.~-1 9.5:1-1:1
w/z 199:1-0.6~:1 lg:l-2:1
w/(x - y ~ z) 19g:l-0.25:1 19:1-0.67~1
a/b 199:1-2.3:1 1~ 4:1
~he degree of polymerization m is such that the Poly~ers I of
the presen~ in~ention have a molecular weight from about 2000 to
about 2 x 106, preferably from about 104 to i~bout 106.
For Polymer II, the degrae of polymQrization n is such that
these polymers have a molecular w~ight of from abou~ 2000 to
about 2 x 106, preferably from about 104 to about 106.
The character of group Q doe~ not signifi~antly affect the
properties o~ the copoly~r. In 50~ cas~s it may pro~ide
polymer hyd~oly~ic s~a~ility or co~pi~tibility with anionlc
sur~actants. Thus, polymer~ with amide groups in the side
chain, e.g., Q is -N~R3-, are usually charac~erized by a :~
better hydrolytic stiability than thoae wi~h es~er groups, e.g.,
. Q is OR3-. Ca~ionic polymers with a ure~hane group, e.g., Q
- is -OR3NHCOOR3-, or a urea group, e.g., Q is
,
:

~ ?~ ~J ~ 1 0
-OR3N~CONHR3-, are characterized by increased compatibility
-~ith anionic surfactants.
Pre~aration of the Monomers
Generally, the Poly~ers I and II are prepared by free
radical polymarization of corresponding monomers.
M~thacrylic acid, potassium 3-sulfopropylmethacrylate,
~imethylaminoethylmethacrylate, dimethylamino~ropyl-
methacrylamide, trimethylpropylmethacrylamide a~monium chloride
were commercial products available from Aldrich Chemical Co. or
Alcolac, Inc.
Urethane and urea-containing monom~rs and their polymers are
prepared from isocyanoethylmethacrylate using syntheses
disclosed in commonly ownad U.S.S.N. 07/481,417 filed February
16, 1990, incorporated herein by reference thereto.
Cationic surfactant mono~srs alkyl-dim~hyl-Cl_4-methacrylate
ammonium h~lides, w~re pr~pared by the qUatQrn~ZatiOn of the
corresponding amines in acQ~onitrile. The products are purified
by recrystallization from acetonitrile.
'
Sulfob2taine-containing ~onomers are prepared by reacting
,~
'
-

2~ ç~.`J~ ll
the corresponding amines with propane sultone. ~he syntheticprocedure is illustrated with the followin~ example:
O=C Q=C
~~ ~ acatonitrile C~
I .,.~_
,S~ ) m-dinitrobenzene
O O ~
,\ ~
S03--
Dimethylaminopropyl methacrylamide (~5.1 ~, 0.5 mole),
~-dinitrobenzene (50.S mg, 3 x 10-4 moles) and 100 ml
acetonitrile were placed in a round-bottom flask placed in an
ice-water bath. Propane sultone (67.13 g, 0.55 mole) dissolved
in 25 ml acetonitrilQ wa~ add~d dropwise and resul~ed in the
formation of white precipita~c. A~ter t~ addition was
completed, the stirring was continued for a few hours at 60 C',
followed by addition of 100 ml of AcOEt. The product was
~iltered off and wa~h~d with acetone.
Synt~esis of ~Q;L~e~;$
All copolym~rization (Polym~r~ I and II) were performed in
an aqueous mediu~ by using pota~iu~ persulfa~e as an
initiator. Typical experim~ntal proce~ureQ are illustrated with
the synthasis of Polymar I-3.
_.
':~
,' ' :~ . ~ '
- ,, . ~,:, .. . .

~ .`L.~-.JX 12
Polymer I-3 (see Table V-Al is prepared as follows: potassium
3-sulfopropylmethacrylate (49.2 g, 0.2 mole), di~ethylamino-
ethylmethacrylate (31.4 g, 0.2 mola) and hexadecyldimethyl-
ethylmethacrylate a~moniu~ bro~ide (17.5 g, 0.038 mole) were
dissolved in 150 g af deionized w2ter~ Potassium persulfate
(500 mq) was addcd and the copolymerization was per~ormed at
c for four hours. The product is a copolymer qel which
can be diluted with water.
Polymers suitable in the practice of the present invention
are illustrated in Ta~les V-A and V-B bQlow (R being -C~3 in
each instance).
. ............ - :.: : -~. .. -
.
. . :
,: . . .

n _ _
~ _ _ ~.
o ~ O ~ --_ _
3 U
m '~
O ~ S O_
o o o u u o u al --no u ~
o o U ~ o U U ~ ~ o -
¢
~I L~
' ~1 IN-- y _
o: o
~ . q h
U ~ ~ ,~ o S
O O t,,l O ~ O Rl 10.
"- a O .......... O ~ u ~ _.,.0O;
C ~V
. .
~ a! 1 ,o.'= O=-~ 0~=~ ^u
X ~ N e7 ~
:
:
: - ~ . - '' : ', :

$.~ J~ .
t~
N t`l
t'
t~l _ t~
U _ o 5~ t3
N N
N t~l
O O
,1 ~ a ~ =~ c ~
U ,., W I ~-
U
ol
- ~
::,

.rr,~
~he following examples are illustrative of the present in~ention.
~xam~le 1
~ his example is illustrativa o~ the suitability of poly~er of tha
invention as hair conditioners.
~ he followin~ compositions were prepared incorporating the Polymer
~enti'ied in Table V-A.
Com~ositions CQncen~ration. w~.
1~ ~ 3 4
Stearalkonium chloridQ 1.0 - ~ ~
Polymer I-l - 1.0 - -
Polymer ~-3 - - 1.0
Polymer I-4 - - - 1.0
Watar ~< Q.S. 100~ >>
*Control incorporating stearalkoniu~ chloride as a
convantional conditioner.
Th~se compo~itions w~re applled ~o dyèd hair tresse~ and
maintained in contac~ with th~ hair ~or 3 minukes, a~ter which
the compo-~itions were ri~sed off. The degree of conditioning a~ :
evalua~ed blindly in two judgme~ts w~o a sessed ~uali~a~ively
the worX to we~ comb ths hair tre~ . The judge~ compar~d : -
t~ese unconditioned tresse~ to an oxidati~rely dyed hair tre55
. ` ` , , -. . . : ..
- ' ~ .' ' ~ ~:
.

~hich was defined as having a scora o~ zan~. The treated hair
_resses were given a rating of between a value of 2ero and 5, ~ha 5
-ating being "very easily combed." The ratings ware made after th~
conditioning tr~atment and again after th~ tr~ated ~r~se~ war~ ~wic~
shampooed. ThQ r~sults are a~ follows.
c~m~osition Condi5ig¢~}---or~ L~Y~39L
Initlal After 2 Sha~Q~
:, o
2 3.75 3.75
o.S 0.5
~ 3.25 0.5
Dyed Hair 0 0
Polym~r I-l has pr~do~inantly.cat~onic charactsr at p~ b~low 10,
contains wsaky acidic carboxyl group~, and has rather low solubility
in the aqueous medium (form~ g~ls). In consQ~uence of this, it can
~ind to hair in r~latively largQ quant~tie3, and is not ea~ily
-emoved by shampooing. In view of its good conditioning prop~rt~
and high durability, Polymer I-l could bQ appropriate. ~or hair
damaged after chs~ical treatm~nts. Polym~r I-4 (Co~position 4) iq
also suitable but does not providQ durabili~y ~-causQ of incrQa~d, ~ ~ -
as compared to Poly~er I-l, solublli~y in water. Thi~ polymer~could
be useful in for~ula~ing day-to-d~y U90 condi~ioner for nor~l or
slightly:dam~gQd hair ~Rcau8~ of its good, a~er-trea~ent
conditioning propertie3, and no build-up charar~eristiCS. Poly~r
r-3 (composition 3) provides a le~er conditioning be~e~i bec u-~ it~
is characterizQd by thQ ov2rall anionic charge above pH 4 and
.
- ~ ,

3~?
17
_elati~ely high solubility in aqueous medi.a. rhis kind o~ a material
s aopropriate for use i~ mild conditioners such as, for exa~pl~, for
-hin and undama~ed hair.
_xample 2
~ he following are examples of conditioning shampoo composition
-ontainlng a polymer of class I of the present in~ention, which
_-mposlt ons are especially useful Cor bleached or dyed hair, e.g.,
-ollowin~ such trea~ments whether at home or in a salon.
Composition 1 2 3 4 S 6
sodiu~ lauryl sulfate16.1615.4515.26 15.04 - -
Sodium lauryl ethQr sulfate - - - o 13.79
~auramide DEA - 5.02 4.96 ~. 5 02 4 52
?olymer I-l 1.57
?olymer I-2 - O.7S - - - -
Polymer I-3 - - 1.49 - -
3MDM hydantoin 0.31 0.30 0.30 0 10 0 30 0 32
.qethyl paraben 0.10 0.10 0.10 0.10 0.10 Ooll
CLtr~c acld 0.63 - 1.19 0.30 - -
~ater ~deionized) <<~ Q.S. 100% >~
pH 4.5 5.5 4.5 4.5 5.5 5.0
For~ulations containing predominantly cationic Polymers I-l,
L-2 and I-4 provid~ greàter conditioning ~hat thosa including
anionic Poly~r I-3. Advantageously, no build-up of polym~rs on
hair surface was obsexv~d after mul~iple shampooing with
Compositions 1-6. Surpr:isingly, ~h~ cationic polymers I-l, I-2
and I-4 were not deac~ivated by the anionic surfactants in the
shampoo composition.
~.
--,

2~ 3~
ExamDle 3
The following are exampl~s of condi.tioning shampoos
containinq polymers in class I, which compositions are
especially used on virgin hair, e.g., aS home shampo~s.
Composition 1 2
Cocoamp~ocarSoxypropionate14.86 14.81
'auramidopropylamine oxide~.76
:auramide DEA '.76 ~.7
Polymer I-2 4.43
Poly~er I-4 - 1.42
DMDM Hydantoin 0.10 0.09
Methyl paraben 0.19 0.19
Water (deionized) <~ Q.S. 100% >>
pH 8 8
Both co~positions, used as shampoos, improve the combability
of untreated hair. Composition 2 pro~ides particularly good
conditioning. I~s ~ffec~ is depend~nt upon th~ duration of
rinsing with water after the 6hampooing, with prolonged rinsin~
reducing the condi=ioning benefit of the treatment.
.
'
: , :

19
~xamPle 4
This example illustrates the utility of the polymers of the
oresent invention in the temporary coloring of hair.
6.2 g of a homogeneous Premix A comprising 16.13% propylene
glycol; 3.~2% methyl paraben and th2 remainder wa~er was
prepared, and blended with 10 g of a 10% solution of Polymer I-3
and also with 70.33 g of Premix B comprising 0.~26~ Natrosol
~50, ~.0426% 2-aminoethylpropanol and the remainder water.
86.53 g of this homoyeneous mixture was blended with i2.98 g o~
a dye mix comprising O.S16% disodium EDTA, ~.287% temporary
dyes, 0.4 g DMDM hydantoin, 0.1 g citric acid and the remaind~r
water.

z ~ $~`~
~ he resulting composition ls a viscous, homo~eneous ~olution
without precipitate. Blended gray hair tress was immersed in
~he formulation, the exces~ of the treatment was squeezed off,
and the hair was dried. Color s~turation was good. A
"bleed-off" test was perfor~ed ~y imm~rsing the hair tress in
water for lS seconds, and then visually evaluating the degree o~
coloration of tha aqu~ous solu~ion. The composition containing
polymer I-3 show~d s~ ll~r ~'blsed-of~" af~ect than compositions
comprising in lieu of ~his poly~er such conventional
~ater-soluble polymers as poly(vinyl pyrrolidone),
?oly(methylvinylether-monoethyl maleate~ (Gantrez), poly(adipic
acid-dimethylaminohydroxypropyldiethylena~riamine) (Cartareten),.
hydroxyethylcellulose or an amphoteric poly~er containing only
(W) and (X) monomQr~, G being -O(C~2)2S03K, Q b~ing
-OCH2CH2-, Rl ea~h being CH3 and w/x - 1. Compositions
containing I-~ and I-6 in lisu of Polym~r I-3 were prepared, and
performed similarly. The re3ults clearly demonstrate superi-
ority of the hydrophobically modi~ied polymers of the present
invention over th~ conventional water-soluble poly~rs, in a
hair dyeing proces~.
Exam~le 5
The Poly~er I-6 ~Table V-A) was used in a 1% aqueous
solution as a hand lotion, and was ~ound to impart good tactile
properties to the tr~!ated skin.
.. - ~ .
.
.
.
: :

2~ ~L~ `~?~
Example 6
rhe rollowing example illustrates the use of Polvmers ~-3
and I-~ as a hair setting agent in an ~erosol composition.
~d~antageously, the compositions do no~t require the
incorporation of a foaming agent such as a low-molecular-weight
surfactant inasmuch as the polymers themselves provide this
functionality.
Concentration,
In~redi~nt Wt.%
?ar~ .~ - Concentrate
Polymer I-3 2
Polymer I-5 - 2
Deionized Water 98 98
Part 8 - Aerosol Product
Concentrate 92 92
Propellant~ 8 8
*3:1 ratio of Fluorocarbon 152A and isobutane.
Discharge of the aerosol product produced a stable,
nonsticky, creamy foam. The product was easily applied to hair
and the hair was easy to comb.
The mousse products o~ the presRn~ invent~on are evaluated
for curl-holding ability by their application to hair unde~
controlled condi~ions. Curl relaxation is then measured on
exposure to high humidity and compare~ with appropriate
standards. For example, 0.3 g of mousse product is applied and
.
. . ~ .
:, . .. .

. J" ~ i. d
spread throughout a 2 g swatch of hair. The hair tress is
curled on a mandrel and dried at ambient conditions. Curl
relaxation that consists of periodic measure~ent o~ the curl
fall is then perfor~ed under exposure to high humidity (90-95%
R.H.). The results presented in the table shown ~elow (percent
and retained as ~ function of time) repre~ent an average per six
hair swatches.
Time _ _ Peroent C4rl Retained
(hours) Control* Com~. 1 Com~. 2
-O- 100 100 100
0.02 61.36 7S.18 70.92
0.5 22.72 39.75 33.52
1 l9.0S 34.91 29.11
2 18.32 31.20 24.~7
3 16.05 26.-89 ~2.15
4 13 . 93 25.68 21.51
6 13.93 23.85 19.61
24 lO.g9 19.52 lS.81
*Water set
Percent curl retained is calculated as follows:
Curl Retention = tL - LtL x 100
(L - Lo~
wherein:
L - the lenq~h o~ hair ~ully extended (standard 6" length).
Lo - the len~th or ~he hair curl i~edia~ely upon
removal fro~ th~ mandrel.
~ = ~he length of the hair curl a~er exposure a~ ti~e t.
This method may also be used a~ dif~erent humidities.
: ' , ', -: ,
'''' ' ~ . . .
'
-