1. A polymer obtained by radical polymerization of a mixture of monomers comprising: - at least one anionic monomer (a) having a polymerizable vinyl group, - at least one nonionic hydrophobic monomer (b) having a polymerizable vinyl group and - one or several cross-linking monomer(s) (c) including at least one compound of formula (I): R O O R1 O (I) n in which: - R is a hydrogen atom or a methyl group, - n is equal to 0 or is an integer from 1 to 30 and - R1 is a C1-C20 linear or branched alkyl group.

2. The polymer according to claim 1, in which the compound of formula (I) is such that R is a hydrogen atom or a methyl group, R1 is a -(CH2)2- group and n is equal to 1.

3. The polymer according to claim 1, in which the compound of formula (I) is such that R is a hydrogen atom and n is equal to 0.

4. The polymer according to any one of the preceding claims, in which said mixture of monomers further comprises at least one monomer (d) having a polymerizable vinyl group and an at least C10, preferably C12 to C36, hydrophobic hydrocarbon chain, which is preferably oxyalkylated, distinct from the monomer (b).

5. The polymer according to any one of the preceding claims, in which said mixture of monomers further comprises at least one additional monomer (e) that is optionally nonionic, distinct from the monomer (b).

6. The polymer according to any one of the preceding claims, in which said anionic monomer(s) (a) are chosen from among the monomers of acrylic acid and/or methacrylic acid and/or one of their salts. 42

7. The polymer according to any one of the preceding claims, in which said anionic monomer(s) (a) represent more than 20% by weight, based on the total weight of monomers forming the polymer.

8. The polymer according to any one of the preceding claims, in which said nonionic hydrophobic monomer(s) (b) are chosen from among C1-C8 alkyl acrylates or C1-C8 alkyl methacrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethyl-hexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and their mixtures.

9. The polymer according to any one of the preceding claims, in which said nonionic hydrophobic monomer(s) (b) represent from 45% to 75% by weight, in particular from 48% to 68% by weight and more particularly from 50% to 64% by weight, based on the total weight of monomers forming the polymer.

10. The polymer according to any one of the preceding claims, in which said mixture of monomers further comprises as cross-linking monomer (c), at least one monomer different from the compound of formula (I), chosen in the group consisting of trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, ethylene glycol di(meth)acrylate, methylenebisacrylamide, triallylcyanurate, diallylphtalate, diallylmaleate and their mixtures.

11. The polymer according to any one of the preceding claims, in which said cross-linking monomer(s) (c) represent less than 5% by weight, based on the total weight of monomers forming the polymer.

12. The polymer according to claim 4, in which said monomer(s) (d) are of formula (II): T-A-Z (II) in which: - T represents a polymerizable group allowing the copolymerization of the monomer (d), - A represents a polymeric chain constituted of: 43 - m units of alkylene oxide of formula -CH2CHR1O- with R1 representing an alkyl group comprising from 1 to 4 carbons, for example an ethyl or methyl group, and m varying from 0 to 150, - p units of alkylene oxide of formula -CH2CHR2O- with R2 representing an alkyl group comprising from 1 to 4 carbons, for example an ethyl or methyl group, and p varying from 0 to 150, - n units of ethylene oxide with n varying from 0 to 150, or from 10 or 15 to 150, or from 10 or 15 to 100, or from 15 to 50, or from 15 to 30, in which the alkylene oxide units of formula -CH2CHR1O-, the alkylene oxide units of formula -CH2CHR2O- and the ethylene oxide units are distributed in blocks, alternating or random and - Z represents a saturated or unsaturated, linear, branched, cyclic or polycyclic, fatty chain of at least 10 carbon atoms, optionally comprising one or several heteroatom(s) such as for example O, S, N or P.

13. The polymer according to claim 4 or 12, in which said monomer(s) (d) represent from 0 to 20% by weight, based on the total weight of monomers forming the polymer.

14. The polymer according to claim 5, in which the additional monomer (e) is chosen from among: - 2-acrylamido-2-methylpropanesulfonic acid and its salts, - the unsaturated telomers of acrylic acid, - the monomers of formula (e1): (e1) in which: - Ra, Rb and Rc represent, independently of one another, H or CH3 and - n is an integer equal to 1 or to 2 and - the monomers of formula (e2): (e2) 44 in which: - Ra’, Rb’, Rc’ and Rd’ represent, independently of one another, H or CH3, - X represents (C=O) or (CH2)r with r=0, 1 or 2, - (AO) represents a polyalkoxylated chain constituted of alkoxylated units, distributed in blocks, alternating or random, chosen from among the ethoxylated units EO, the propoxylated units PO and the butoxylated units BO and - q is equal to 0 or represents an integer varying from 1 to 150.

15. A method for the preparation, by radical polymerization, of a polymer as defined according to any one of claims 1 to 14, comprising at least the step consisting of polymerizing a mixture of: - at least one anionic monomer (a) having a polymerizable vinyl group, - at least one nonionic hydrophobic monomer (b) having a polymerizable vinyl group, - one or several cross-linking monomer(s) (c) including at least one compound of formula (I): R O O R1 O (I) n in which: - R is a hydrogen atom or a methyl group, - n is equal to 0 or is an integer from 1 to 30 and - R1 is a C1-C20 linear or branched alkylene group, - optionally at least one monomer (d) having a polymerizable vinyl group and an at least C10, preferably C12 to C36, hydrophobic hydrocarbon chain, which is preferably oxyalkylated, distinct from the monomer (b) and - optionally at least one additional monomer (e) that is optionally nonionic, distinct from the monomer (b).

16. The method according to claim 15, further comprising at least the following subsequent step: - polymerization, in the presence of the polymer P1 obtained previously at the end of the method according to claim 15, of a second mixture of monomers allowing the obtention of a second polymer P2 comprising: - at least one anionic monomer (a’) having a polymerizable vinyl group, 45 - at least one nonionic hydrophobic monomer (b’) having a polymerizable vinyl group, - one or several cross-linking monomer(s) (c’) including at least one compound of formula (I): R O O R1 O (I) n in which: - R is a hydrogen atom or a methyl group, - n is equal to 0 or is an integer from 1 to 30 and - R1 is a C1-C20 linear or branched alkylene group, - optionally at least one monomer (d’) having a polymerizable vinyl group and an at least C10, preferably C12 to C36, hydrophobic hydrocarbon chain, which is preferably oxyalkylated, distinct from the monomer (b’) and - optionally at least one additional monomer (e’) that is optionally nonionic, distinct from the monomer (b’).

17. An aqueous composition comprising at least one polymer as defined according to any one of claims 1 to 14 or as obtained according to the method of claim 15 or 16.

18. A use of a monomer of formula (I): R O O R1 O (I) n in which: - R is a hydrogen atom or a methyl group, - n is equal to 0 or is an integer from 1 to 30 and - R1 is a C1-C20 linear or branched alkylene group, in an amount of less than 5% by weight, based on the total weight of monomers forming the polymer, for the preparation of a polymer.

F O R M 2
THE PATENTS ACT, 1970
(39 of 1970)
COMPLETE SPECIFICATION
(See section 10 and rule 13)
1. TITLE OF THE INVENTION
POLYMER AS THICKENER AND SUSPENDING AGENT
2. APPLICANT(S)
(a) NAME
(b) NATIONALITY
(c) ADDRESS
COATEX
FRENCH Company
35, RUE AMPÈRE,
F-69730 GENAY,
FRANCE
3. PREAMBLE TO THE DESCRIPTION
PROVISIONAL
The following specification describes invention
COMPLETE (√)
The following specification particularly describes the invention
and the manner in which it is to be performed
4. DESCRIPTION (Description shall start from next page)
5. CLAIMS (not applicable for provisional specification. Claims should start with the preamble – “I/We claim”
on separate page)
6. DATE AND SIGNATURE ( to be given on the last page of specification)
7. ABSTRACT OF THE INVENTION (to be given along with complete specification on the separate page)
Note:
*Repeat boxes in case of more than one entry
*To be signed by the applicant(s)or the authorized registered patent agent
*Name of the applicant should be given in full, family name in the beginning
*Complete address of the applicant should be given stating with postal index no. / code, state and country
*Strike out the column which is/are not applicable
2
The present invention relates to novel polymers that may be used as rheology modifying agents
for aqueous formulations and which can induce not only good thickening and clearness
properties, but also good suspending performances.
Rheology modifying agents, also known as thickening agents or viscosity modifying agents, are
present in cleaning compositions, whether this be in personal care or hygiene compositions, for
example cosmetic compositions, or in maintenance compositions such as detergent products.
These agents have an influence on the rheological properties (in particular viscosity) and esthetic
properties (such as the clearness) of the formulation, which is generally rich in surfactants, and
also on the capacity for suspending and stabilizing particles within the formulation.
Among the rheology modifying agents commonly used in aqueous formulations, mention may
be made of alkali-soluble or swellable polymers, more commonly known by the abbreviation
“ASE” (for “Alkali-Soluble or SwellableEmulsions”) and
hydrophobically-modified alkali-soluble or swellablepolymers, more commonly known by the
abbreviation “HASE” (for “Hydrophobically-modified Alkali-Soluble or SwellableEmulsions”).
Thus, documents such as US2006/0271563, WO2014/090709 and CN104292378 describe
aqueous compositions integrating polymers of this type as rheology modifying agents.
Document US 4309330 describes a copolymer in emulsion obtained from a dicyclopentadiene
derivative, an unsaturated monomer, a hydroxylated unsaturated monomer and another monomer
with an isocyanate function, which is useful for the preparation of a cross-linked coating.
Document US 2012/0231056 describes a method for thickening a formulation by modifying its
pH. This formulation is obtained from a copolymer prepared in direct emulsion and in the
absence of cross-linking monomer.
Formulators are constantly in search of access to novel agents having the abovementioned
properties and, as far as possible, improved properties in terms of performances, especially over
a wide pH range.
The present invention aims precisely at satisfying these objects. Thus, it aims at proposing novel
rheology modifying agents, which not only have good properties in terms of thickening effect
(viscosity), but also make it possible to give formulations that have good suspending properties
and high clearness (clear continuous phase), and which can do so over a wide pH range.
3
The inventors have discovered that it is possible to access to a formulation that satisfies all these
criteria (viscosity, suspension performances and clearness) by using a specific polymer as
rheology modifying agent. More particularly, the present invention relates, according to a first of
its aspects, to a polymer obtained by radical polymerization of a mixture of monomers
comprising:
- at least one anionic monomer (a) having a polymerizable vinyl group,
- at least one nonionic hydrophobic monomer (b) having a polymerizable vinyl group and
- one or several cross-linking monomer(s) (c) including at least one compound of formula
(I):
R
O
O R1 O
(I) n
in which:
- R is a hydrogen atom or a methyl group,
- n is equal to 0 or is an integer from 1 to 30, for example from 1 to 20, or for example
from 1 to 15, or for example from 1 to 10, and
- R1 is a C1-C20 linear or branched alkyl group.
Advantageously, as illustrated in the examples that follow, the polymers according to the
invention give the aqueous formulation in which they are used good suspension, thickening and
clearness properties, and do so over a wide pH range, i.e. equally well at acidic, neutral and
basic pH values.
Typically, a polymer according to the invention is obtained by radical polymerization of a
mixture of monomers comprising:
- more than 20% by weight, based on the total weight of monomers forming the polymer
of at least one anionic monomer (a) having a polymerizable vinyl group;
- 45% to 75% by weight, based on the total weight of monomers forming the polymer of at
least one nonionic hydrophobic monomer (b) having a polymerizable vinyl group; and
- less than 5% by weight, based on the total weight of monomers forming the polymer of
one or several cross-linking monomer(s) (c) including at least one compound of formula
(I) as defined below.
4
The term “suspending properties” or “suspending power” is intended to denote the ability of the
composition to maintain in suspension particles in its continuous phase, in particular stably over
time, for example during storage of the composition.
For the purposes of the invention, the term “particles” to be suspended is intended to denote
solid, filled or hollow bodies, but also liquid species that are immiscible with the continuous
phase of the formulation or encapsulated or gaseous species which may be characterized by
different shapes, textures, structures, compositions, colors and final properties. As a guide,
mention may be made of exfoliant particles (for example polyethylene particles, pounded fruit
shells or pumice), nourishing particles (for example collagen spheres), nacreous particles (for
example mica titanium, glycol distearates) and esthetic particles (for example air bubbles, flakes
or pigments, which are optionally colored). As regards the suspension of air bubbles in the
composition, the particles may especially have a size of 1, 2 or 3 mm.
The suspension performances may be evaluated by applying a “suspension applicating test” by
determining in particular the elastic modulus value G’, the Tan (δ)value and the elastic
resistance value, as described in the examples that follow.
The “clearness” or “clarity” of the composition may be evaluated by measuring the
transmittance of the composition. A method for determining the transmittance is described in the
examples that follow. It is expressed as a percentage. A composition is considered as being clear
or limpid if it has a transmittance, for a wavelength of 500 nm, of at least 60%, preferably of at
least 70% and even more preferentially of at least 80%.
Other characteristics, advantages and modes of application of the polymer according to the
invention will emerge more clearly on reading the description and the examples that follow,
which are given as a non limiting illustration.
In the text hereinbelow, the expressions “between … and …”, “ranging from … to …” and
“varying from … to …” are equivalent and are intended to mean that limits are included, unless
otherwise mentioned.
5
Unless otherwise mentioned, the term “comprising one” should be understood as “comprising at
least one”.
DESCRIPTION OF A POLYMER ACCORDING TO THE INVENTION
As indicated previously, the polymer according to the invention obtained by radical
polymerization of a mixture of monomers comprises:
- at least one anionic monomer (a) having a polymerizable vinyl group,
- at least one nonionic hydrophobic monomer (b) having a polymerizable vinyl group and
- one or several cross-linking monomer(s) (c) including at least one compound of formula
(I):
R
O
O R1 O
(I) n
in which:
- R is a hydrogen atom or a methyl group,
- n is equal to 0 or is an integer from 1 to 30, for example from 1 to 20, or for example
from 1 to 15, or for example from 1 to 10, and
- R1 is a C1-C20 linear or branched alkyl group.
Preferably according to the invention, the polymer according to the invention does not contain
any hydroxylated monomer having a polymerizable vinyl group or else does not contain any
monomer having an isocyanate group.
Also preferably according to the invention, the polymer according to the invention is obtained
by radical polymerization of a mixture of monomers consisting of:
- at least one anionic monomer (a) having a polymerizable vinyl group,
- at least one nonionic hydrophobic monomer (b) having a polymerizable vinyl group and
- one or several cross-linking monomer(s) (c) including at least one compound of formula
(I):
R
O
O R1 O
(I) n
in which:
6
- R is a hydrogen atom or a methyl group,
- n is equal to 0 or is an integer from 1 to 30, for example from 1 to 20, or for example
from 1 to 15, or for example from 1 to 10, and
- R1 is a C1-C20 linear or branched alkyl group.
Also preferably according to the invention, n is an integer from 1 to 30, for example from 1 to
20, or for example from 1 to 15, or for example from 1 to 10.
In the text hereinbelow, the proportions of monomers entering in the composition of the polymer
according to the invention are expressed as weight percentages based on the total weight of
monomers used to form the polymer.
According to a particular embodiment, the polymer according to the invention does not
comprise any monomer unit other than the monomers (a), (b), and (c) (with the exception of the
optional presence of fragments of transfer agents or of polymerization initiators).
In other words, according to one embodiment variant, the sum of the contents of monomers (a),
(b) and (c) in the composition of the polymer according to the invention is equal to 100%.
According to another embodiment, the polymer according to the invention may also comprise
one or several additional monomer unit(s) distinct from the monomers (a), (b) and (c).
In particular, the composition of the polymer according to the invention may also comprise one
or several monomer(s) (d) having a polymerizable vinyl group and a hydrophobic hydrocarbon
chain and/or one or several additional nonionic monomer(s) (e) as detailed more specifically in
the text hereinbelow.
The monomers (a), (b), (c), (d) and (e) in the composition of the polymer according to the
invention are different. In particular, said monomer(s) (b) are different from said monomer(s) (d)
and/or from said monomer(s) (e).
According to a particular embodiment, the polymer according to the invention is a multiphasic
polymer.
7
For the purposes of the invention, the term “multiphasic polymer” is intended to denote a
multiphasic polymer particle, in other words a polymer particle having a non homogeneous
composition, prepared via a sequential polymerization method in at least two steps from at least
two compositions (or mixtures) of distinct monomers.
As will be presented hereinbelow, on conclusion of the first step, a first polymer, referred to
hereinbelow as polymer P1, is obtained by radical polymerization from a first mixture of
monomers (a), (b) and (c) and optionally (d) and/or (e), and then, at the end of the second step, a
second polymer, referred to hereinbelow as polymer P2, is obtained by radical polymerization
from a second mixture of monomers (a’), (b’) and (c’) and optionally (d’) and/or (e’).Given that
(a’) is a nonionic monomer having a polymerizable vinyl group, (b’) is a nonionic hydrophobic
monomer having a polymerizable vinyl group, (c’) is one or several cross-linking monomer(s)
optionally including a compound of formula (I), (d’) is a monomer having a polymerizable vinyl
groupand an at least C10hydrophobic hydrocarbon chain (distinct from (b’)), and (e’) is an
optionally nonionic additional monomer (distinct from (b’)).
According to this particular embodiment, the multiphasic particles according to the invention
may especially be core/shell structured, the first polymer forming the “core” and the second
polymer forming the “shell”. This “core/shell” name should not, however, be interpreted as
denoting a particle in which the “core” part is totally covered or encapsulated with a “shell” part,
but as denoting a particle of controlled morphology having two distinct phases.
Thus, for the purposes of the invention, the term “polymer according to the invention”
comprises both a polymer obtained by radical polymerization of a single mixture of monomers
as defined below, and a multiphasic polymer within the meaning of the present invention, i.e.
formed from several polymer compositions including at least one polymer composition P1 and
one polymer composition P2 as detailed hereinbelow.
For the purposes of the present invention, the term “polymer composition P1” and the term
“polymer P1” are denoted without distinction.
For the purposes of the present invention, the term “polymer composition P2” and the term
“polymer P2” are denoted without distinction.
8
The term “polymer P1” may be understood as a single polymer P1 as defined above or several
polymers P1 obtained by sequential polymerization.
Similarly, the term “polymer P2” may be understood as a single polymer P2 as defined above or
several polymers P2 obtained by sequential polymerization.
According to a particular embodiment, the polymer P1 does not comprise any monomer units
other than the monomers (a), (b) and (c) (with the exception of the optional presence of
fragments of transfer agents or of polymerization initiators).
According to a particular embodiment, the polymer P2 does not comprise any monomer units
other than the monomers (a’), (b’) and (c’) (with the exception of the optional presence of
fragments of transfer agents or of polymerization initiators).
In other words, according to an embodiment variant, the sum of the contents of monomers (a),
(b) and (c) in the composition of the polymer P1 (respectively (a’), (b’) and (c’) in the
composition of the polymer P2) is equal to 100%.
According to another embodiment, the polymer P1 and/or the polymer P2 may also comprise
one or several additional monomer unit(s) distinct from the monomers (a), (b) and (c)
(respectively (a’), (b’) and (c’)).
In particular, the composition of the polymer P1 (respectively of the polymer P2) may also
comprise one or several monomer(s) (d) (respectively (d’)) having a polymerizable vinyl group
and a hydrophobic hydrocarbon chain and/or one or several optionally nonionic additional
monomer(s) (e) (respectively (e’)) as detailed more specifically in the text hereinbelow).
Moreover, it is understood that the monomers (a) and (a’) (respectively (b) and (b’), respectively
(c) and (c’), respectively (d) and (d’), respectively (e) and (e’)) entering in the composition of
the polymer P1 and of the polymer P2 may be of the same nature in the polymer P1 and in the
polymer P2, or of different nature.
9
The monomers (a), (b), (c), (d) and (e) in the composition of the polymer P1 are different. In
particular, said monomer(s) (b) are different from said monomer(s) (d) and/or from said
monomer(s) (e). This is likewise the case for the monomers (a’), (b’), (c’), (d’) and (e’) in the
composition of the polymer P2.
According to a particular embodiment, the polymer P1/polymer P2 weight distribution of the
multiphasic polymer according to the invention is between 45/55 and 95/5, in particular between
60/40 and 90/10.
Anionic monomer having a polymerizable vinyl group, known as “monomer (a)”
According to a particular embodiment, the anionic monomers (a) (and (a’)) having a
polymerizable vinyl group, referred to more simply in the text hereinbelow as “anionic
monomers”, comprise at least one carboxylic group.
In particular, the anionic monomers may be chosen from acrylic acid, methacrylic acid, maleic
acid, itaconic acid, crotonic acid and their mixtures, and/or the salts of these acids.
According to a particular embodiment, the anionic monomers may be chosen from among
acrylic acid and/or methacrylic acid monomers and/or one of their salts.
According to another embodiment, the anionic monomers may be chosen from among acrylic
acid and/or methacrylic acid monomers.
Preferably, the anionic monomer of the polymer according to the invention is methacrylic acid
(MAA).
Said anionic monomer(s) may represent more than 20% by weight, for example at least 23% by
weight, or for example at least 25% by weight, in particular from 25% to 50% by weight, and
more particularly from 27% to 41% by weight, based on the total weight of monomers forming
the polymer.
According to a particular embodiment, when the polymer according to the invention is a
multiphasic polymer:
10
- said anionic monomer(s) (a) may represent more than 20% by weight, for example at
least 23% by weight, or for example at least 25% by weight, in particular from 25% to
50% by weight, and more particularly from 27% to 41% by weight, based on the total
weight of monomers forming the polymer P1, and
- said anionic monomer(s) (a’) may represent more than 20% by weight, for example at
least 23% by weight, or for example at least 25% by weight, in particular from 25% to
50% by weight, and more particularly from 26% to 35% by weight, based on the total
weight of monomers forming the polymer P2.
According to yet another embodiment, the mass proportion of monomer (a’) in the polymer P2
(mass content of monomers (a’) based on the total weight of monomers forming the polymer P2)
is less than that in the polymer P1 (mass content of monomers (a) based on the total weight of
monomers forming the polymer P1).
Nonionic hydrophobic monomer having a polymerizable vinyl group, known as “monomer
(b)”
The nonionic hydrophobic monomers (b) (and (b’)) having a polymerizable vinyl group, referred
to more simply in the text hereinbelow as “nonionic hydrophobic monomers”, are monomers not
having any positive charge or any negative charge in aqueous solution.
They may be chosen from among esters, amides or nitriles of acrylic or methacrylic acids or
from among acrylonitrile, styrene, methylstyrene, diisobutylene, vinylpyrrolidone or
vinylcaprolactam.
Most particularly, the nonionic hydrophobic monomers may be chosen from among C1-C8alkyl
acrylates or C1-C8 alkyl methacrylates, such as methyl acrylate, ethyl acrylate (also known as
EA in the text hereinbelow), butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl
methacrylate, butyl methacrylate and their mixtures.
According to a particular embodiment, the nonionic hydrophobic monomers may be chosen
from among methyl acrylate, ethyl acrylate, butyl acrylate, ethyl methacrylate and their
mixtures.
11
In particular, the nonionic hydrophobic monomer of the polymer according to the invention may
be ethyl acrylate.
Said nonionic hydrophobic monomer(s) may represent from 45% to 75% by weight, in
particular from 48% to 68% by weight and more particularly from 50% to 64% by weight, based
on the total weight of monomers forming the polymer according to the invention.
Said anionic monomer(s) and said nonionic hydrophobic monomer(s) may represent more than
83% by weight, in particular between 83% and 99.8% or between 85% and 99.6% by weight of
the overall composition of the polymer of the invention.
The term “overall composition” means the total weight of the monomers used for the synthesis
of the polymer according to the invention.
According to a particular embodiment, the polymer according to the invention is such that:
- the anionic monomer is chosen from among acrylic acid and/or methacrylic acid and/or
one of their salts; for example, it is chosen from among acrylic acid and/or methacrylic
acid; in particular, this monomer is methacrylic acid, and
- the nonionic hydrophobic monomer is chosen from among methyl acrylate, ethyl
acrylate, butyl acrylate, ethyl methacrylate and their mixtures, in particular this monomer
is ethyl acrylate.
According to a particular embodiment, when the polymer according to the invention is a
multiphasic polymer, said nonionic hydrophobic monomer(s) (b) may represent from 45% to
75% by weight, in particular from 48% to 65% by weight and more particularly from 50% to
60% by weight, based on the total weight of monomers forming the polymer P1 and said
nonionic hydrophobic monomer(s) (b’) may represent from 45% to 75% by weight, in particular
from 50% to 68% by weight and more particularly from 55% to 64% by weight, based on the
total weight of monomers forming the polymer P2.
According to a particularly preferred embodiment, the mass proportion of monomers (b’) in the
polymer P2 (mass content of monomers (b’) based on the total weight of monomers forming the
12
polymer P2) is greater than that in the polymer P1 (mass content of monomers (b) based on the
total weight of monomers forming the polymer P1).
According to one embodiment, the nonionic hydrophobic monomers (b’)/anionic monomers (a’)
weight distribution in the composition of the polymer P2 is between 60/40 and 85/15, in
particular between 65/35 and 80/20.
According to a particular embodiment, the nonionic hydrophobic monomers (b)/anionic
monomers (a) weight distribution in the composition of the polymer P1 is between 53/47 and
70/30, in particular between 55/45 and 68/32.
Cross-linking monomer including at least one compound of formula (I), known as
“monomer (c)”
The mixture of monomers compliant with the invention also comprises one or several crosslinking
monomer(s) (c) including at least one compound of formula (I) as defined below.
According to a particular embodiment, when the polymer according to the invention is a
multiphasic polymer, the mixtures of monomers leading to the polymer P1 and to the polymer
P2 both also comprise one or several cross-linking monomer(s)(c) and (c’), respectively, only
one of the monomers (c) and (c’) comprising at least one compound of formula (I) as defined
below. Thus, according to this embodiment, either the mixture of monomers leading to the
polymer P1 or the mixture of monomers leading to the polymer P2 comprises a compound of
formula (I) as defined below.
According to another particular embodiment, when the polymer according to the invention is a
multiphasic polymer, the mixtures of monomers leading to the polymer P1 and to the polymer
P2 both also comprise one or several cross-linking monomer(s)(c) and (c’), respectively, each of
the monomers (c) and (c’) comprising at least one compound of formula (I) as defined below.
The cross-linking monomers (c) and (c’)are referred to more simply in the text hereinbelow as
“cross-linking monomers”.
13
According to a particular embodiment, the polymer according to the invention comprises as
cross-linking monomer only one compound of formula (I).
According to another embodiment, it comprises two different cross-linking monomers including
at least one compound of formula (I).
According to yet another embodiment, it comprises three different cross-linking monomers
including at least one compound of formula (I).
The cross-linking monomer(s) are used to generate a polymer in the form of a
three-dimensional network.
The compound of formula (I) and the optional additional cross-linking monomer(s) are defined
below.
(a) Compound of formula (I)
As presented previously, the mixtures of monomers compliant with the invention necessarily
comprise as cross-linking monomer at least one compound of formula (I):
R
O
O R1 O
(I) n
in which:
- R is a hydrogen atom or a methyl group,
- n is equal to zero or is an integer from 1 to 30, for example from 1 to 20, or for example
from 1 to 15, or for example from 1 to 10, and
- R1is a C1-C20 linear or branched alkyl group.
It is understood that the ester-ether chain may be linked to the tricyclo[5.2.1.02.6]decenyl ring
either via the carbon atom of the tricycle featured above or via the carbon atom of the tricycle
located below the bond starting from the oxygen atom of the group -[R1-O]n-.
According to one embodiment, the compound of formula (I) is such that R is a hydrogen atom or
a methyl group, R1is a -(CH2)2- group, and n is 1.
14
According to another embodiment, the compound of formula (I) is such that R is a hydrogen
atom and n is equal to zero.
According to yet another embodiment, the compound of formula (I) is chosen from among:
- ethylene glycol dicyclopentenylether methacrylate (also known as ethylene glycol
tricyclo[5.2.1.02.6]decene methacrylate, EGDCPEMA, for instance Fancryl FA-512MTM
orFancryl FA-512MTTMsold by the company Hitachi Chemical),
- ethylene glycol dicyclopentenylether acrylate (also known as ethylene glycol
tricyclo[5.2.1.02.6]deceneacrylate, EGDCPEA, for instance Fancryl FA-512ASTMsold by
the company Hitachi Chemical),
- dicyclopentenylether acrylate (also known as tricyclo[5.2.1.02.6]decene acrylate, for
instance Fancryl FA-511AASTMsold by the company Hitachi Chemical) and
- their mixtures, for example the mixture of EGDCPEA and of EGDCPEMA.
According to yet another embodiment, the compound of formula (I) is EGDCPEA.
According to yet another of its aspects, the present invention relates to the use of a monomer of
formula (I):
R
O
O R1 O
(I) n
in which:
- R is a hydrogen atom or a methyl group,
- n is equal to zero or is an integer from 1 to 30, for example from 1 to 20, or for example
from 1 to 15, or for example from 1 to 10, and
- R1is a C1-C20 linear or branched alkyl group,
in an amount of less than 5% by weight based on the total weight of monomers forming the
polymer, to prepare a polymer, in particular to prepare a polymer whose composition is defined
above.
The present invention also relates to the use of a monomer of formula (I):
R
O
O R1 O
(I) n
15
in which:
- R is a hydrogen atom or a methyl group,
- n is equal to zero or is an integer from 1 to 30, for example from 1 to 20, or for example
from 1 to 15, or for example from 1 to 10, and
- R1is a C1-C20 linear or branched alkyl group,
in an amount of less than 5% by weight based on the total weight of monomers forming the
polymer, to cross-link a polymer/mixture of monomers, in particular to cross-link a mixture of
monomers as mentioned above.
(b) Additional cross-linking monomer(s)
As indicated above, the mixtures of monomers compliant with the invention may, besides a
compound of formula (I) as cross-linking monomer, also comprise another or several other
additional cross-linking monomer(s) (c) distinct from the compound of formula (I) as defined
previously.
According to a particular embodiment, the polymer according to the invention comprises only
one other cross-linking monomer distinct from the compound of the formula (I).
According to another embodiment, it comprises two different cross-linking monomers, distinct
from the compound of formula (I).
According to the present invention, use is made, as additional cross-linking monomer distinct
from a compound of formula (I), of a monomer which is a polyunsaturated compound. This
compound may comprise two, three or several ethylenic unsaturations.
The additional cross-linking monomer may have hydrophilic, hydrophobic or amphiphilic
nature.
Examples of these compounds include di(meth)acrylate compounds such as polyalkylene glycol
di(meth)acrylate, especially polypropylene glycol di(meth)acrylate, ethylene glycol
di(meth)acrylate, polyethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1,3-
butylene glycol di(meth)acrylate, 1,6-butylene glycol di(meth)acrylate, 1,6-hexanediol
di(meth)acrylate, neopentyl glycol
di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, but also 2,2’-bis(4-
16
(acryloxypropyloxyphenyl)propane, 2,2'-bis(4-(acryloxydiethoxyphenyl)propane and zinc
acrylate; tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate and
ethoxylated trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate,
pentaerythritol tri(meth)acrylate and trimethylolmethane tri(meth)acrylate; tetra(meth)acrylate
compounds such as ditrimethylolpropane tetra(meth)acrylate, tetramethylolmethane
tetra(meth)acrylate and pentaerythritol tetra(meth)acrylate; hexa(meth)acrylate compounds such
as dipentaerythritolhexa(meth)acrylate; penta(meth)acrylate compounds such as
dipentaerythritolpenta(meth)acrylate; allylic compounds such as allyl (meth)acrylate, diallyl
phthalate, diallylitaconate, diallyl fumarate, diallyl maleate and triallylcyanurate; polyallyl ethers
of sucrose containing from 2 to 8 groups per molecule, polyallyl ethers of pentaerythritol such as
pentaerythritoldiallyl ether, pentaerythritoltriallyl ether and pentaerythritoltetraallyl ether;
trimethylolpropanepolyallyl ethers such as trimethylolpropanediallyl ether and
trimethylolpropanetriallyl ether. Other polyunsaturated compounds include divinyl glycol,
divinylbenzene, divinylcyclohexyl and methylenebisacrylamide.
According to another aspect, the additional cross-linking monomers may be prepared via an
esterification reaction of a polyol with an unsaturated anhydride such as maleic anhydride or
itaconic anhydride or via an addition reaction with an isocyanate such as
3-isopropenyldimethylbenzene isocyanate.
Use may also be made of the following compounds to obtain additional cross-linking monomers:
polyhaloalkanolssuch as 1,3-dichloroisopropanol and 1,3-dibromoisopropanol;
haloepoxyalkanessuch as epichlorohydrin, epibromohydrin, 2-methylepichlorohydrin and
epiiodohydrin; polyglycidyl ethers such as 1,4-butanediol diglycidylether, glycerol 1,3-
diglycidyl ether, ethylene glycol diglycidylether, propylene glycol diglycidylether, diethylene
glycol diglycidylether, neopentyl glycol diglycidylether, polypropylene glycol diglycidylether,
bisphenol A-epichlorohydrinepoxy resin and mixtures.
According to a particular embodiment, the additional cross-linking monomers usedin the
polymer according to the invention are chosen from trifunctional cross-linking agents.
They may be in particular trimethylolpropanetri(meth)acrylate (TMPTA) or ethoxylated
trimethylolpropane tri(meth)acrylate (for instance TMPTA 3OE).
17
According to one embodiment, the mixture of monomers that is suitable for use in the invention
also comprises as cross-linking monomer (c) at least one monomer different from the compound
of formula (I), chosen from the group consisting of trimethylolpropane
tri(meth)acrylate,ethoxylated trimethylolpropane tri(meth)acrylate, ethylene glycol
di(meth)acrylate, methylenebisacrylamide, triallylcyanurate, diallylphthalate, diallyl maleate and
their mixtures.
According to another embodiment, the mixture of monomers compliant with the invention
comprises as cross-linking monomers two distinct monomers, namely EGDCPEA and TMPTA.
According to yet another embodiment, the mixture of monomers compliant with the invention
comprises as cross-linking monomers two distinct monomers, namely EGDCPEA and TMPTA
3OE.
Said cross-linking monomer(s) may represent less than 5% by weight, in particular from 0.2% to
4.5%, more particularly from 0.25% to 1.15% by weight, and even more particularly from
0.40% to 1.05% by weight, based on the total weight of monomers forming the polymer
according to the invention.
Monomer having a polymerizable vinyl group and a hydrophobic hydrocarbon chain,
known as “monomer (d)”
The mixture of monomers compliant with the invention may also comprise at least one
monomer (d) (or (d’)) having a polymerizable vinyl group and an at least C10, preferably C12to
C36, hydrophobic hydrocarbon chain, which is preferably oxyalkylated, distinct from the
monomer (b) (or (b’)) if it is the monomer (d’)).
These monomers may be more particularly chosen from among monomers of formula (II)
below:
T-A-Z (II)
in which:
- T represents a polymerizable group allowing the copolymerization of the monomer (d)
(or(d’)),
- A represents a polymeric chain constituted of:
18
- m units of alkylene oxide of formula -CH2CHR1O- with R1 representing an alkyl group
comprising from 1 to 4 carbons, for example an ethyl or methyl group, and m varying
from 0 to 150,
- p units of alkylene oxide of formula -CH2CHR2O- with R2 representing an alkyl group
comprising from 1 to 4 carbons, for example an ethyl or methyl group, and p varying
from 0 to 150,
- n units of ethylene oxide with n varying from 0 to 150, or from 10 or 15 to 150, or from
10 or 15 to 100, or from 15 to 50, or from 15 to 30,
in which the alkylene oxide units of formula -CH2CHR1O-, the alkylene oxide units of
formula -CH2CHR2O- and the ethylene oxide units are distributed in blocks, alternating
or random and
- Z represents a saturated or unsaturated, linear, branched, cyclic or polycyclic, fatty chain of
at least 10 carbon atoms, for example a C12 to C36 chain, optionally comprising one or
several heteroatom(s) such as for example O, S, N or P.
According to a preferred embodiment, the sum of m, p and n is not zero.
The term “propoxylated units PO” and “butoxylated units BO” means ethoxylated units bearing
on one or other of their carbons a methyl or ethyl radical, respectively. An ethoxylated unit is a –
CH2-CH2-O unit.
The term “fatty chain” means an aliphatic hydrocarbon chain of a fatty acid, which is linear,
branched, cyclic or polycyclic, comprising at least 10 carbon atoms, for example from 12 to 36
carbon atoms, optionally comprising one or several heteroatom(s)such as for example O, S, N or
P.
According to one embodiment, the chain Z is a branched chain comprising 16 carbon atoms.
The end T more particularly represents a radical containing a polymerizable unsaturated group,
belonging to the group of acrylic, methacrylic, maleic, itaconic or crotonic esters. The end T
may especially be chosen from among acrylate, methacrylate, allylic, vinyl,
methacrylurethaneand ,-dimethyl-m-isopropenyl benzyl urethane groups.
19
According to one embodiment, the monomer (d) or (d’) corresponds to formula (III) below:
CH2=C(R1)-COO-A-Z (III)
inwhich:
- R1 represents H or CH3and
- A and Z have the same definition as in formula (II) above.
According to a particular embodiment, A in the abovementioned formulae (II) and (III)
represents a polymer chain consisting of 15 to 150, in particular from 15 to 50 and especially
from 15 to 30 ethylene oxide units.
As examples, the monomer (d) (or (d’)) may correspond to formula (II) or (III) in which A and Z
are such that:
- m and p are equal to zero, n is equal to 25, R1 represents CH3, Z is a branched chain
comprising 16 carbon atoms, namely 2-hexyl-1-decanyl,
- m and p are equal to zero, n is equal to 25, R1 represents CH3, Z is a branched chain
comprising 32 carbon atoms,
- m and p are equal to zero, n is equal to 25, R1 represents CH3, Z is a linear chain
comprising 22 carbon atoms,
- m and p are equal to zero, n is equal to 36, R1 represents CH3, Z is a branched chain
comprising 20 carbon atoms, namely 2-octyl-1-dodecyl, or
- m and p are equal to zero, n is equal to 30, R1 represents CH3, Z is an oxo chain
comprising 12 carbon atoms.
According to one particular embodiment, when the polymer according to the invention is a
multiphasic polymer, said monomer(s) (d) may be present only in the polymer P1.
According to another particular embodiment, when the polymer according to the invention is a
multiphasic polymer, said monomer(s) having a polymerizable vinyl group and a hydrophobic
hydrocarbon chain (named (d’) in that case) may be present only in the polymer P2.
Alternatively, said monomer(s) (d) and (d’) may be present both in the polymer P1 and in the
polymer P2 of the multiphasic polymer of the invention.
20
Said monomer(s) (d), and optionally (d’), may represent from 0 to 20% by weight, in particular
from 1 to 15% by weight, and more particularly from 2 to 12% by weight, based on the total
weight of monomers forming the polymer according to the invention.
In particular, said monomer(s) (d) may be used in a proportion of at least 0.5% by weight, in
particular from 0.5 to 12% by weight, based on the total weight of monomers forming the
polymer P1.
In particular, said monomer(s) (d’) may be used in a proportion of at least 0.5% by weight, in
particular from 0.5 to 12% by weight, based on the total weight of monomers forming the
polymer P2.
Optionally nonionic additional monomer, known as “monomer (e)”
The mixture of monomers compliant with the invention may also comprise at least one
additional monomer (e) (or (e’)), which is optionally nonionic, distinct from the monomer (b)
(or (b’) if it is the monomer (e’)).
These optionally nonionic additional monomers (e) and (e’)may be chosen more particularly
from among:
- 2-acrylamido-2-methylpropanesulfonic acid (especially such as the product sold under
the name AMPS® by the company Lubrizol) and its salts,
- the unsaturated telomers of acrylic acid,
- the monomers of formula (e1):
(e1)
in which:
- Ra, Rb and Rc represent, independently of one another, H or CH3 and
- n is an integer equal to 1 or to 2 and
- the monomers of formula (e2):
(e2)
21
in which:
- Ra’, Rb’, Rc’ and Rd’ represent, independently of one another, H or CH3,
- X represents (C=O) or (CH2)r with r=0, 1 or 2,
- (AO) represents a polyalkoxylated chain constituted of alkoxylated units, distributed in
blocks, alternating or random, chosen from among the ethoxylated units EO, the
propoxylated units PO and the butoxylated units BO and
- q is equal to 0 or represents an integer varying from 1 to 150.
In particular, the additional monomers of formula (e1) may be chosen from among allyl alcohol
(n=1), methallyl alcohol (n=1) and isoprenol (n=2). For example, the optional monomer is
isoprenol.
The term “unsaturated telomers of acrylic acid” means oligomers of acrylic acid or of
acryloxypropionic acid, of formula (IV):
(IV)
wheren is an integer varying from 1 to 10. These various oligomers may be in a mixture. When
n = 1, the oligomer is an acrylic acid dimer.
It is understood that the various particular embodiments described for each of the anionic
monomers, nonionic hydrophobic monomers, cross-linking monomers, monomers having a
polymerizable vinyl group and a hydrophobic hydrocarbon chain and optionally nonionic
additional monomers of the polymer according to the invention may be combined.
Said optionally nonionic additional monomer(s) (e) and optionally (e’) may represent less than
50% by weight, in particular less than 40% by weight and more particularly from 1% to 30% by
weight, based on the total weight of monomers forming the polymer according to the invention.
According to a particular embodiment, the polymer according to the invention is obtained from a
mixture of monomers comprising at least the following monomers:
22
- one or several anionic monomer(s) chosen from among acrylic acid and/or methacrylic
acid and/or one of their salts, preferably acrylic acid and/or methacrylic acid, in
particular methacrylic acid,
- one or several nonionic hydrophobic monomer(s) chosen from among methyl acrylate,
ethyl acrylate, butyl acrylate, ethyl methacrylate and their mixtures, in particular ethyl
acrylate,
- one or several cross-linking monomer(s) as defined previously including at least one
compound of formula (I) chosen from among ethylene glycol dicyclopentenylether
methacrylate, ethylene glycol dicyclopentenylether acrylate, dicyclopentenylether
acrylate and their mixtures, preferably EGDCPEA, EGDCPEMA and their mixtures, in
particular EGDCPEA,
- optionally one or several monomer(s) having a polymerizable vinyl group and a
hydrophobic hydrocarbon chain as described previously and
- optionally one or several optionally nonionic additional monomer(s) as defined
previously.
METHOD FOR PREPARING A POLYMER ACCORDING TO THE INVENTION
The polymer according to the invention may be prepared via conventional polymerization
techniques starting especially from the monomers (a), (b), (c) and optionally (d), (e) and one or
several other cross-linking monomer(s) distinct from a compound of formula (I) as defined
previously.
According to one embodiment, the polymer according to the invention may be obtained by
emulsion, dispersion or solution radical polymerization.
According to another embodiment, the polymer according to the invention is obtained by
emulsion radical polymerization.
Polymerization is carried out in suitable solvents, in the presence of known initiators.
By way of example, the polymerization initiator may be a persulfate salt, such as ammonium
persulfate.
23
The emulsion radical polymerization may be carried out in the presence of at least one surfactant
and optionally of at least one chain-transfer agent, for regulating the molecular mass of the
chains produced during the polymerization.
As surfactants that may be used, mention may be made of:
- anionic surfactants, such as for example a fatty acid salt, an alkyl sulfate salt (such as
sodium lauryl sulfate), an alkyl ether sulfate salt (such as sodium lauryl ether sulfate), an
alkylbenzenesulfonate salt (such as sodium dodecylbenzenesulfonate), an alkyl
phosphate salt or a sulfosuccinate diester salt, a cocoamphoacetate salt (such as sodium
cocoamphoacetate), a cocoamphodiacetatesalt (such as sodium cocoamphodiacetate), a
lauroylglutamate salt (such as sodium lauroyl glutamate), acocoyl isethionate salt (such
as sodium cocoyl isethionate), a lauroyl methyl isethionate salt (such as sodium lauroyl
methyl isethionate), a methyl cocoyltaurate salt (such as sodium methyl cocoyltaurate), a
methyl oleyltaurate salt (such as sodium methyl oleyltaurate), a lauroylsarcosinate salt
(such as sodium lauroylsarcosinate), a laureth-3 sulfosuccinate salt (such as sodium
laureth-3 sulfosuccinate), a cocoyl apple amino acid salt (such as sodium cocoyl apple
aminate), a cocoyl oat amino acid salt (such as sodium cocoyl oat aminate),
- nonionic surfactants, such as for example a polyoxyethylene alkyl ether or a
polyoxyethylene fatty acid ester,
- cationic surfactants, such as for examplequaternary alkyl- and/or
aryl-ammonium halides,
- zwitterionic or amphoteric surfactants, such as for examplesurfactants comprising a
betaine group, and
- their mixtures.
As chain-transfer agents, mention may be made advantageously of mercaptan compounds
comprising at least four carbon atoms, such as butyl mercaptan, noctylmercaptan,n-dodecylmercaptan
andtert-dodecyl mercaptan.
The emulsion polymerization is conventionally carried outin an aqueous dispersion medium.
Thus, according to another of its aspects, the invention relates to a method for the preparation
via radical polymerization of a polymer as defined previously, comprising at least the step
consisting of polymerizing a mixture of:
24
- at least one anionic monomer (a) having a polymerizable vinyl group,
- at least one nonionic hydrophobic monomer (b) having a polymerizable vinyl group,
- one or several cross-linking monomer(s) (c) including at least one compound of formula
(I):
R
O
O R1 O
(I) n
in which:
- R is a hydrogen atom or a methyl group,
- n is equal to 0 or is an integer from 1 to 30, for example from 1 to 20, or for example
from 1 to 15, or for example from 1 to 10, and
- R1 is a C1-C20 linear or branched alkyl group,
- optionally at least one monomer (d) having a polymerizable vinyl group and an at least C10,
preferably C12 to C36, hydrophobic hydrocarbon chain, which is optionally oxyalkylated,
distinct from the monomer (b) and
- optionally at least one additional monomer (e) that is optionally nonionic, distinct from the
monomer (b).
The polymer of the invention may also be polymerized via an inverse emulsion synthesis. With
this technique, the monomers are dissolved in water, the acidic anionic monomer(s) being
optionally partially or totally neutralized. This solution of the monomers is then emulsified in a
solvent, for instance a mixture of alkanes or a petroleum fraction, or a mixture of synthetic or
natural oils. The synthesis of the polymer is then carried out using water-soluble initiators,
allowing polymerization within each emulsion droplet in the continuous oily phase. This
technique also makes it possible to obtain polymers with a higher mean molecular mass than via
direct emulsion polymerization in water.
The polymer of the invention may also be polymerized via a solvent phase synthesis. With this
technique, the monomers are dissolved in a solvent or mixture of solvents, such as chlorinated
solvents, aromatic solvents or other volatile solvents. The polymerization is then carried out
using initiators that are soluble in the solvent. The polymer chains precipitate during their
growth in the form of a pulverulent solid, which is then separated out by filtration, the residual
solvents then being removed by evaporation under vacuum. This technique also makes it
25
possible to obtain polymers with a higher mean molecular mass than via direct emulsion
polymerization in water.
According to a particular embodiment, when the polymer according to the invention is a
multiphasic polymer, it may be prepared sequentially, by emulsion, dispersion or solution
radical polymerization, preferably in at least two consecutive steps as explained hereinbelow, the
first step being as defined previously and allowing the production of a first polymer P1.
Preferably, the multiphasic polymer according to the invention is prepared by radical
polymerization in at least two steps, the polymer P1 and the polymer P2 being produced in two
sequential emulsion polymerization steps, in particular in this order: P1 and then P2.
The polymerization is carried out under suitable conditions as described previously.
Thus, according to a particular embodiment, a method according to the invention also comprises
at least the following subsequent step:
- polymerization, in the presence of the polymer P1 obtained previously at the end of the
method as described previously, of a second mixture of monomers allowing the
obtention of a second polymer P2 comprising:
- at least one anionic monomer (a’) having a polymerizable vinyl group,
- at least one nonionic hydrophobic monomer (b’) having a polymerizable vinyl group,
- one or several cross-linking monomer(s) (c’) including at least one compound of formula
(I):
R
O
O R1 O
(I) n
in which:
- R is a hydrogen atom or a methyl group,
- n is equal to 0 or is an integer from 1 to 30, for example from 1 to 20, or for example
from 1 to 15, or for example from 1 to 10, and
- R1 is a C1-C20 linear or branched alkyl group,
26
- optionally at least one monomer (d’) having a polymerizable vinyl group and an at least C10,
for example C12 to C36, hydrophobic hydrocarbon chain, which is optionally oxyalkylated,
distinct from the monomer (b’) and
- optionally at least one additional monomer (e’) that is optionally nonionic, distinct from the
monomer (b’).
From a practical viewpoint, the first step consists in placing the monomers intended to enter in
the composition of the polymer P1 in contact with a polymerization initiator, this placing in
contact possibly being carried out in discontinuous mode, or in batch mode, or in semi-batch
mode or in semi-continuous mode (the placing in contact being carried out over a period that
may range from several minutes to several hours).
From a practical viewpoint, the second step (step of preparing the polymer P2) may take place in
the following manner:
- a step of adding the monomers intended to enter in the composition of the polymer P2 to
a dispersion medium comprising the already-formed polymer P1, this addition possibly
taking place in a discontinuous mode, a batch mode, a semi-batch mode or a semicontinuous
mode (the placing in contact being carried out over a period which may range
from several minutes to several hours) and
- simultaneously for the semi-continuous mode or subsequent to this addition step for the
discontinuous mode, a step of introducing a polymerization initiator.
APPLICATIONS OF A POLYMER ACCORDING TO THE INVENTION
The polymers according to the invention prove to be particularly efficient as rheology modifying
agentsin a wide range of aqueous compositions. Mention may be made of aqueous compositions
in varied industrial fields and especially fracking fluids in drilling, ceramic formulations, and
paper coating colors. Mention is made in particular of washing compositions containing
surfactants, such as personal care or home care compositions. The term “personal care
compositions” comprises, for example, cosmetic compositions, personal hygiene compositions,
toiletry products and cleaning compositions for application to the body (including the skin, the
hair and the nails) of humans or animals, for example shampoo compositions. The term “home
care compositions” includes compositions used for cleaning or maintaining sanitary conditions,
for example in the kitchen, the bathroom, detergent products, laundry products, etc.
27
Thus, according to yet another of its aspects, the invention relates to an aqueous composition
comprising at least one polymer according to the invention or as obtained according to the
method described above.
The polymer according to the invention may be used in the aqueous composition in a proportion
of from 0.1% to 20% by weight, in particular from 0.5% to 12% by weight, based on the total
weight of the composition.
As illustrated in the examples that follow, the polymer according to the invention
advantageously makes it possible to combine performances in terms of thickening effect,
clearness and suspending properties. In other words, it allows the production of an aqueous
composition having the desired viscosity and comprising a limpid continuous phase and
particles in suspension distributed homogeneously in the continuous phase.
The invention thus more particularly relates to the use of a polymer according to the invention or
as obtained according to a method as defined previously in an aqueous composition as a
thickening and suspending agent.
Thus, advantageously, the polymer according to the invention may be used in
surfactant-rich formulations such as the abovementioned detergent and cosmetic compositions.
The invention also relates to the use for the preparation of a stable aqueous composition,
comprising a limpid continuous phase and particles in suspension distributed in the continuous
phase, of a polymer as defined previously.
The invention also relates to an agent for obtaining a stable aqueous composition, comprising a
limpidcontinuous phase and particles in suspension distributed in the continuous phase,
comprising a polymer according to the invention.
In addition to the clearness it provides, the agent of the invention thus makes it possible to
maintain in suspension the particles present in the composition. The use of a composition thus
formulated therefore does not require any mixing step, even if the composition has been stored
for several weeks, or even several months.
28
A composition according to the invention may comprise ingredients conventionally used in the
formulations mentioned previously. It may comprise one or several active ingredient(s) (or
active agent(s)), in any form whatsoever, and irrespective of the field of application of the
composition, as indicated previously. The active principle(s) may be dissolved in the continuous
phase of the composition and/or they may be in particulate form, which is insoluble in the
continuous phase, and constitute all or some of the particles in suspension.
It may comprise one or several surfactant(s), chosen in particular from among anionic,
zwitterionic or amphoteric, cationic or nonionic surfactants, and their mixtures.
The invention relates more particularly to an aqueous cosmetic composition, comprising a
continuous phase and particles in suspension in the continuous phase, said continuous phase
and/or said particles comprising and/or consisting of a cosmetic active principle, said
composition comprising a polymer as defined previously.
As active principle(s), it may comprise a washing base for the body and/or the hair.
Advantageously, the rheology modifying agent according to the invention makes it possible to
access to the desired viscosity, clearness and suspending effect properties for a wide pH range,
of not only acidic, but also neutral or basic pH values.
This wide pH range includes, needless to say, the mean pH value of human skin. The rheology
modifying agent according to the invention is thus of major cosmetic interest.
The invention will now be described by means of the examples that follow, which are obviously
given as nonlimiting illustrations of the invention.
EXAMPLES
The following abbreviations are used:
MAA: methacrylic acid
EA: ethyl acrylate
MA: monomer(d) of formula (III) in which m and p are equal to zero, n is equal to 25,
R1represents CH3, Z is a branched chain comprising 16 carbon atoms, namely 2-hexyldecanyl
29
MA1:monomer (d) of formula (III) in which m and p are equal to zero, n is equal to 25, R1
represents CH3, Z is a branched chain comprising 32 carbon atoms, namely 2-tetradecyloctadecanyl

MA2: monomer (d) of formula (III) in which m and p are equal to zero, n is equal to 25, R1
represents CH3, Z is a linear chain comprising 22 carbon atoms, namely docosyl
MA3:monomer (d) of formula (III) in which m and p are equal to zero, n is equal to 36, R1
represents CH3, Z is a branched chain comprising 20 carbon atoms, namely 2-octyldodecanyl
MA4:monomer (d) of formula (III) in which m and p are equal to zero, n is equal to 30, R1
represents CH3, Z is an oxo chain comprising 12 carbon atoms
FA-512AS (sold by the company Hitachi): ethylene glycol dicyclopentenylether acrylate
(EGDCPEA)
FA-512MT (sold by the company Hitachi): ethylene glycol dicyclopentenylether methacrylate
(EGDCPEMA)
FA-511AAS (sold by the company Hitachi): dicyclopentenylether acrylate (DCPEA)
SR 351 (sold by the company Sartomer): trimethylolpropanetriacrylate (TMPTA)
SR 454 (sold by the company Sartomer): trimethylolpropanetriacrylate 3OE (TMPTA 3OE)
TMPDE 90 (sold by the company Perstorp): trimethylolpropanediallylether (TMPDAE)
SR DFM (sold by the company Sartomer): monomethacrylicTMPDAE
SIPOMER® HPM100 (sold by the company Rhodia): nopol methacrylate 10OE
VISIOMER® EGDMA SG (sold by the company Evonik): ethylene glycol dimethacrylate
(EDMA).
Example of synthesis of polymers in a semi-batch method
The protocolfor synthesizing the polymer carried outin semi-batch mode is as follows:
432 g of deionized water and 9.29 g of a solution containing 28% by mass of sodium lauryl ether
sulfate are placed in a stirred 1L reactor heated with an oil bath.
The premix comprising the following ingredients:
- ethyl acrylate: 196.1 g,
- methacrylic acid: 99.67 g,
- macromonomer noted as MA: 25.96 g,
- EGDCPEA: 1.38 g,
- deionized water: 172.5 g and
30
- solution containing 28% of sodium lauryl ether sulfate: 6.47 g
is prepared in a beaker.
This premix is stirred so as to form an emulsion.
A solution consisting of 0.1167 g of sodium persulfate and 5 g of deionized water, known as
“initiator 1”, is prepared.
A solution consisting of 0.3 g of sodium persulfate and 50 g of deionized water, known as
“initiator 2”, is prepared.
Initiator 1 is injected when the reactor is heated to a temperature of 86°C + 2°C.
Next, the solution of polymerization initiator 2 is injected into the reactor over
2 hours and the monomer premix is injected into the reactor over 2 hours, in parallel.
35 g of water are then added.
The resulting mixture is heated for a further one hour at a temperature of 86°C + 2°C.
The whole is then cooled to room temperature.
Example of synthesis of multiphasicpolymers
The protocol for synthesizing the multiphasic polymer is as follows:
430 g of deionized water and 9.29 g of a solution containing 28% by mass of sodium lauryl ether
sulfate are placed in a stirred 1L reactor heated with an oil bath.
The premix P1 comprising the following ingredients:
- ethyl acrylate: 131.74 g,
- methacrylic acid: 81.86 g,
- macromonomer noted as MA: 19.82 g,
- EGDCPEA: 1.05 g,
- deionized water: 139.1 g and
- solution containing 28% of sodium lauryl ether sulfate: 4.93 g
is prepared in a beaker.
This premix is stirred so as to form an emulsion.
The premix P2 comprising the following ingredients:
- ethylacrylate: 54.75 g,
- methacrylic acid: 26.74 g,
- macromonomer noted as MA: 6.14 g,
- EGDCPEA: 0.33 g,
- deionized water: 42.8 g and
31
- solution containing 28% of sodium lauryl ether sulfate: 1.54 g
is prepared in a beaker.
This premix is stirred so as to form an emulsion.
A solution consisting of 0.318 g of sodium persulfate and 5 g of deionized water, known as
initiator 1, is prepared.
A solution consisting of 0.269 g of sodium persulfate and 50 g of deionized water, known as
initiator 2, is prepared.
Initiator 1 is injected when the reactor is heated to a temperature of 86°C + 2°C.
Next, the solution of polymerization initiator 2 is injected into the reactor over 2 hours and, in
parallel, the premix P1 of monomers is injected into the reactor over 90 minutes, followed by the
premix P2 over 30 minutes.
35 g of water are then added.
The resulting mixture is heated for a further 1 hour at a temperature of 86°C + 2°C.
The whole is then cooled to room temperature.
All the polymers presented in the examples that follow were synthesized under the conditions
described above, varying the compositions of monomers in the monomer premixes.
The composition of the polymer is indicated as a weight percentage of each of the monomers
based on the total weight of monomers forming the polymer.
Similarly, when it is a multiphasic polymer, the composition of the polymer P1 and,
respectively, that of the polymer P2 is indicated as a weight percentage of each of the monomers
based on the total weight of the monomers of P1 and, respectively, of P2.
Evaluation in an aqueous formulation
The polymers are tested in an aqueous formulation, having the composition indicated in table 1
below (2.4% or 3% by weight of polymer based on the total weight of the composition).
Compounds Amount (wt.%)
Sodium lauryl ether sulfate (SLES) 9
Cocamidopropylbetaine (CAPB) 3
Test polymer 2.4 or 3
Water qsp 100
Table 1
The pH of the formulation is adjusted to a value of 5, 6 or 7 by adding lactic acid or sodium
hydroxide.
32
Properties evaluated
The compositions are evaluated for their clearness, viscosity and suspending
performancesproperties.
Clearness
The clearness of the composition is evaluated by measuring the transmittance according to the
following protocol:
The measurements are taken on a Genesys 10 UV™UVspectrometer (Cole Parmer),equipped
with Rotilabo-EinmalKuvetten PS, 4.5 mL cuvettes. In practice, the machine is preheated for 10
minutes before use. A first measurement is first taken using a cuvette filled with 3.8 mL of
double-deionized water (the “blank”). The measurement is then taken with a cuvette filled with
3.8 mL of the solution of cosmetic composition to be tested. The transmittance is then measured
at a wavelength of 500 nm. The higher the transmittance value, expressed as a percentage, the
clearer the cosmetic composition.
As indicated previously, it is considered that at a transmittance value at 500 nm of at least 60%,
the composition is limpid.
Viscosity
The viscosity of said formulations is measured using a Brookfield, LVT model viscometer.
Before measuring the viscosity, each of the formulations is left to stand for 24 hours at 25°C.
The spindle must be centered relative to the aperture of the flask.
The viscosity is then measured at 6 rpm (rotations per minute) using the appropriate module.
The viscometer is left rotating until the viscosity is stable.
The rheology modifying agent should give a sufficient viscosity to the formulation in which it is
used. In general, the viscosity desired for the thickened formulations is greater than 4,000 mPa.s,
in particular greater than 6,000 mPa.s and more particularly greater than 8,000 mPa.s.
Suspending performances
Viscoelasticity measurements are taken on said formulations using a Haake-Mars III rheometer.
The Tan(δ) and G’ variations as a function of the stress (sweep from 0 to 1000dyn/cm2
) are
measured at 25°C using 1° cone/plate geometry. The Tan(δ) and G’ values at 10 dyn/cm2
are
extrapolated and the elastic resistance value is deduced from this measurement.
33
In general, the stability of particles introduced into said formulations is observed for combined
values of G’ > 60 Pa, Tan(δ) < 0.55 and elastic resistance> 70 dyn/cm2
.
EXAMPLE 1: Polymers according to the invention
The polymers tested, named pol.1 to pol.20, illustrated in tables 2 to 6, are polymers according
to the invention which were synthesized according to the protocols detailed above.
More specifically, pol.1 to pol.14 are polymers prepared according to the semi-batch method,
whereas the polymers pol.15 to pol.20 are multiphasic polymers.
In particular, it should be noted that:
- pol. 1 and pol.2, given in table 2, are polymers not comprising any monomer (d),
- pol.3 to pol.9 and pol.15 to pol.20, given in tables 2, 3 and 5, are polymers comprising
various cross-linking monomers (c) and
- pol.10to pol.14, given in table 4, are polymers comprising various monomers (d).
Polymers tested Pol. 1 Pol. 2 Pol.3 Pol.4 Pol.5
Overall
composition
EA 64.00 63.82 62.52 62.52
MAA 35.40 35.26 34.54 34.54
MA - - 2.04 2.04
Cross-linking
agent (c)
0.60
EGDCPEA
0.92
EGDCPEA
0.90
EGDCPEA
0.90
EGDCPEMA
0.90
DCPEA
3% active agent,
pH=7
G’ (Pa) 97 70 77 91
Tan (δ) 0.36 0.40 0.54 0.54
Elastic
resistance
(dyn/cm2
)
110 80 110 120 115
T(500nm) (%) 98 96 97 98 93
Brook.visco.
(mPa.s)
17500 8700 15400 19900
18200
3% active agent,
pH = 6
Brook.visco.
(mPa.s)
25300 25700 29000 29000
28500
3% active agent,
pH = 5
Brook.visco.
(mPa.s)
12200 12300 16500 16500 17600
Table 2
34
Table 3
Polymers tested Pol. 10 Pol.11 Pol. 12 Pol. 13 Pol.14
Overall
composition
EA 60.67 60.67 60.67 60.67 60.67
MAA 31.10 31.10 31.10 31.10 31.10
Monomer (d) 7.80
MA
7.80
MA1
7.80
MA2
7.80
MA3
7.80
MA4
EGDCPEA 0.43 0.43 0.43 0.43
2.4% active
agent, pH=6
G’ (Pa) 119 109 100 173 92
Tan (δ) 0.33 0.30 0.40 0.42 0.26
Elastic resistance
(dyn/cm2
)
150 110 110 300 100
T(500nm) (%) 93 80 94 91 91
Brook.visco. (mPa.s) 19200 16000 21100 45100 12300
2.4% active
agent, pH=5
G’ (Pa) 97 81 96 149 65
Tan (δ) 0.34 0.26 0.34 0.33 0.29
Elastic resistance
(dyn/cm2
)
130 85 105 220 80
T(500nm) (%) 91 66 91 83 86
Brook.visco. (mPa.s) 16000 10300 17300 32700 9800
Table 4
Polymers tested Pol.6 Pol.7 Pol.8 Pol.9
Overall
composition
EA 60.44 60.80 60.3
MAA 30.91 31.10 31.00 31.00
MA 7.80 7.80 7.80 7.80
Cross-linking agent (c)
0.85
EGDCPEA
0.30
EGDCPEA
0.90
EGDCPEA +
TMPTA
(50/50)
0.90
EGDCPEA +
TMPTA 3OE
(50/50)
2.4% active
agent, pH=6
G’ (Pa) 120 75 108 126
Tan (δ) 0.30 0.45 0.31 0.30
Elastic resistance
(dyn/cm2
)
115 120 110 120
T(500nm) (%) 89 95 90 90
Brook.visco. (mPa.s) 17400 16400 17400 19300
2.4% active
agent, pH = 5
G’ (Pa) 107 66 105 109
Tan (δ) 0.30 0.44 0.31 0.30
Elastic resistance
(dyn/cm2
)
110 90 110 110
T(500nm) (%) 85 93 87 87
Brook.visco.(mPa.s) 15700 14000 15100 16300
35
Polymers tested Pol. 15 Pol. 16
Composition P1
EA 60.34 60.17
MAA 36.79 36.69
MA 2.17 2.17
Cross-linking agent (c) 0.70
EGDCPEA
0.97
EGDCPEMA
CompositionP2
EA 67.70 68.15
MAA 29.20 29.40
MA 1.72 1.73
Cross-linking agent (c) 1.38
EGDCPEA
0.72
EGDCPEMA
Overall composition
EA 62.52 62.52
MAA 34.54 34.54
MA 2.04 2.04
Cross-linking agent (c) 0.90 0.90
Proportion P1 70.40 70.60
Proportion P2 29.60 29.40
3% active agent,
pH = 7
G’ (Pa) 83 68
Tan (δ) 0.51 0.51
Elastic resistance (dyn/cm2
) 115 95
T(500nm) (%) 97 97
Brook.visco. (mPa.s) 17100 20400
3% active agent,
pH = 6
Brook.visco. (mPa.s) 29700 29500
3% active agent,
pH = 5
Brook.visco. (mPa.s) 13300 14600
Table 5
Polymers tested Pol. 17 Pol. 18 Pol. 19 Pol. 20
Composition
P1
EA 55.92 56.16 55.92 55.92
MAA 35.00 35.16 35.00 35.00
MA 8.19 8.23 8.19 8.19
Cross-linking agent (c) 0.89
EGDCPEA
0.45
EGDCPEA
0.89
EGDCPEMA
0.89
DCPEA
Composition
P2
EA 62.00 62.23 62.00 62.00
MAA 30.50 30.61 30.50 30.50
MA 6.76 6.79 6.76 6.76
Cross-linking agent (c) 0.74
EGDCPEA
0.38
EGDCPEA
0.74
EGDCPEMA
0.74
DCPEA
Overall
composition
EA 57.58 57.82 57.58 57.58
MAA 33.77 33.92 33.77 33.77
MA 7.80 7.83 7.80 7.80
Cross-linking agent (c) 0.85 0.43 0.85 0.85
Proportion P1 72.74 72.72 72.74 72.74
Proportion P2 27.26 27.28 27.26 27.26
36
2.4% active
agent, pH=6
G’ (Pa) 94 141 97 73
Tan (δ) 0.29 0.28 0.30 0.47
Elastic resistance (dyn/cm2
) 85 150 100 75
T(500nm) (%) 78 88 81 94
Brook. visco. (mPa.s) 11800 19500 13200 8700
2.4% active
agent, pH=5
G’ (Pa) 140 139 144 121
Tan (δ) 0.25 0.25 0.24 0.25
Elastic resistance (dyn/cm2
) 120 150 130 120
T(500nm) (%) 69 80 69 65
Brook. visco. (mPa.s) 14600 18700 15300 13500
Table 6
The results presented in tables 2 to 6 show that the polymers according to the invention not only
have good properties in terms of thickening, but also make it possible to obtain formulations that
have good suspending performances and high clearness for all of the polymers tested.
In addition, the results given in table 3 for pol.8 and pol.9 show that it is possible to use an
additional cross-linking monomer (c),in the present case TMPTA or TMPTA 3OE, in addition to
a compound of formula (I), in the present case EGDCPEA.
EXAMPLE 2: Polymers outside the invention
The polymers tested, named C1 to C9, illustrated in tables 7 to 10, are polymers outside the
invention which were synthesized according to the protocols detailed above and which comprise
cross-linking monomers not in accordance with those used in the present invention. More
particularly, the polymers C1 to C6 are polymers prepared according to the semi-batch method,
whereas the polymers C7 to C9 are multiphasic polymers.
Polymers tested
C1
outside the invention
C2
outside the
invention
C3
outside the invention
Overall
composition
EA 63.54 62.52 62.52
MAA 35.56 34.54 34.54
MA - 2.04 2.04
Cross-linking agent
(c)
0.90
TMPTA +
TMPDAE (75/25)
0.90
TMPTA
0.90
TMPTA +
monomethacrylicTMPDAE
(63/37)
37
3% active
agent, pH=7
G’ (Pa) 29 44 49
Tan (δ) 0.56 0.90 0.58
Elastic resistance
(dyn/cm2
)
30 55 40
T(500nm) (%) 92 98 97
Brook. visco. (mPa.s) 5100 14000 9100
3% active
agent, pH=6
Brook. visco. (mPa.s) 23600 8800 24300
3% active
agent, pH=5
Brook. visco. (mPa.s) 14500 5300 14400
Table 7
Polymers tested C4outside the invention C5outside the invention
Overall
composition
EA 62.52 62.52
MAA 34.54 34.54
MA 2.04 2.04
Cross-linking agent (c) 0.90
5-vinyl-2-norbornene
0.90
nopol methacrylate 10 OE
3% active agent,
pH = 7
G’ (Pa) 52 55
Tan (δ) 1.23 1.88
Elastic resistance (dyn/cm2
) 40 120
T(500nm) (%) 95 99
Brook. visco. (mPa.s) 3800 20100
3% active agent,
pH = 6
Brook. visco. (mPa.s) 8220 1530
3% active agent,
pH = 5
Brook. visco. (mPa.s) 4880 2970
Table 8
Polymers tested C6 outside the invention
Overall
composition
EA 60.44
MAA 30.91
MA 7.80
Cross-linking agent (c) 0.85
TMPTA
2.4% active
agent, pH = 6
G’ (Pa) 42
Tan (δ) 0.58
Elastic resistance (dyn/cm2
) 50
T(500nm) (%) 94
Brook. visco. (mPa.s) 12400
2.4% active
agent, pH = 5
G’ (Pa) 32
Tan (δ) 0.58
Elastic resistance (dyn/cm2
) 40
38
T(500nm) (%) 92
Brook. visco. (mPa.s) 10800
Table 9
Polymers tested
C7 outside the
invention
C8outside the invention
C9 outside
the invention
Composition
P1
EA 55.92 55.92 55.92
MAA 35.00 35.00 35.00
MA 8.19 8.19 8.19
Crosslinking

agent (c)
0.89
EDMA
0.89
Tricyclodecanedimethanoldimethacrylate
0.89
5-vinyl-2-
norbornene
Composition
P2
EA 62.00 62.00 62.00
MAA 30.50 30.50 30.50
MA 6.76 6.76 6.76
Crosslinking

agent (c)
0.74
EDMA
0.74
Tricyclodecanedimethanoldimethacrylate
0.74
5-vinyl-2-
norbornene
Overall
composition
EA 57.58 57.58 57.58
MAA 33.77 33.77 33.77
MA 7.80 7.80 7.80
Crosslinking

agent (c)
0.85
EDMA
0.85
Tricyclodecanedimethanoldimethacrylate
0.85
5-vinyl-2-
norbornene
Proportion P1 72.74 72.74 72.74
Proportion P2 27.26 27.26 27.26
2.4% active
agent,
pH = 6
G’ (Pa) 28 26 Not
determinable
Tan (δ) 0.71 0.78 Not
determinable
Elastic
resistance
40 40 Not
determinable
T(500nm) 95 97 55
Brook. 7900 8100 1100
2.4% active
agent,
pH = 5
G’ (Pa) 28 25 Not
determinable
Tan (δ) 0.65 0.68 Not
determinable
Elastic
resistance
40 35 Not
determinable
T(500nm) 94 95 45
Brook. 9000 8700 3100
Table 10
39
In general, the results given in tables 7 to 10 show that the properties of the polymers
(thickening effect, suspending performances and clearness) vary according to the nature of the
cross-linking monomer used not compliant with the invention.
Certain comparisons, by way of example, are illustrated in the following section.
For example, by comparing compliant pol.6 (EGDCPEA) and non-compliant C6 (TMPTA), it is
observed that the formulation comprising pol.6 has better suspending properties (significantly
higher G’ value and lower Tan (δ) value), a clearness of the same order of magnitude and
viscosity values that are higher overall than a formulation comprising C6 or TMPTA.
By comparing compliant pol.2 (EGDCPEA) and non-compliant C1 (TMPTA + TMPDAE
(75/25)), it is observed that the formulation comprising pol.2 has better suspending properties,
and also a clearness and viscosity values of the same order of magnitude at pH 6 and 5 compared
to a formulation comprising C1 or TMPTA/TMPDAE.
By comparing compliant pol.3, pol.4, pol.5, pol.15 or pol.16 with non-compliant C2 or C3, it is
observed that the formulations comprising the compliant polymers have better suspending
properties and a clearness of the same order of magnitude.
By comparing compliant pol.3, pol.4, pol.5, pol.15 or pol.16 with non-compliant C4, it is
observed that the formulations comprising the compliant polymers have higher viscosity values.
By comparing compliant pol.17, pol.19 or pol.20 with non-compliant C7 or C8, it is observed
that the formulations comprising the compliant polymers have better suspending properties, a
higher viscosity and a clearness of the same order of magnitude.
Finally, by comparing compliant pol.17, pol.19 or pol.20 with non-compliant C9, it is observed
that the formulations comprising the compliant polymers have better clearness and a higher
viscosity.
EXAMPLE 3: Ultra-mild scrubbing shower gel
This example illustrates the use of agents according to the invention in cosmetic formulations of
ultra-mild shower gel type, and serves to demonstrate the rheological properties (suspension and
viscosity) and organoleptic properties afforded according to the invention.
Thus, using a shower gel formulation based on anionic and zwitterionic surfactants, the
composition of which is given in table 11, the aim consisted in checking in this formulation the
clearness, the viscosity and the suspension as influenced by various rheology modifying agents
including reference products and those according to the invention.
40
1-DI water (double-deionized water) qsp 100
2-Texapon® NSO UP (BASF) 32.14
3-Dehyton® PK 45 (BASF) 6.67
4-Rheology modifying agent Polymer tested at 3%
5-Sodium hydroxide qs pH = 7.0 ± 0.1
6-Potassium sorbate (Nutrinova) 0.40
7-Strawberry Fragrance (Hyteck) 0.50
8-Exfoson® Quin 300 red, exfoliant particles (Soniam) 2.00
Table 11
Protocol for preparing the formulation:
The double-deionized water (1) is introduced in a beaker, and the various ingredients (2) and (3)
are then added with stirring.
- After homogenization is complete, the rheology modifying agent (4) is added with very
moderate stirring.
- The pH is measured, and is then adjusted to 7.0 ± 0.1 with the ingredient (5).
- After checking the pH, the preserving agent (6) and the fragrance (7) are mixed with
moderate stirring into the shower gel formulation.
- Finally, the quinoa exfoliant particles (8) are dispersed with stirring.
Table 12 collates all of the rheology modifying agents that were used as ingredient (4) in the
context of the tests of the present example 3.
In table 12:
REF: REFerence/INV: INVention/OINV: Outside INVention.
REF INV OINV
NaCl Pol. 15 C3
Brookfield viscosity 6 rpm (mPa.s) 17,800 17,100 9,100
Tan (δ) 12 0.51 0.58
Elastic resistance (dyn/cm2
) 0 115 40
T(500 nm) (%) 98 97 97
Table 12
41
WE CLAIM:
1. A polymer obtained by radical polymerization of a mixture of monomers comprising:
- at least one anionic monomer (a) having a polymerizable vinyl group,
- at least one nonionic hydrophobic monomer (b) having a polymerizable vinyl group
and
- one or several cross-linking monomer(s) (c) including at least one compound of
formula (I):
R
O
O R1 O
(I) n
in which:
- R is a hydrogen atom or a methyl group,
- n is equal to 0 or is an integer from 1 to 30 and
- R1 is a C1-C20 linear or branched alkyl group.
2. The polymer according to claim 1, in which the compound of formula (I) is such that R
is a hydrogen atom or a methyl group, R1 is a -(CH2)2- group and n is equal to 1.
3. The polymer according to claim 1, in which the compound of formula (I) is such that R
is a hydrogen atom and n is equal to 0.
4. The polymer according to any one of the preceding claims, in which said mixture of
monomers further comprises at least one monomer (d) having a polymerizable vinyl
group and an at least C10, preferably C12 to C36, hydrophobic hydrocarbon chain, which is
preferably oxyalkylated, distinct from the monomer (b).
5. The polymer according to any one of the preceding claims, in which said mixture of
monomers further comprises at least one additional monomer (e) that is optionally
nonionic, distinct from the monomer (b).
6. The polymer according to any one of the preceding claims, in which said anionic
monomer(s) (a) are chosen from among the monomers of acrylic acid and/or methacrylic
acid and/or one of their salts.
42
7. The polymer according to any one of the preceding claims, in which said anionic
monomer(s) (a) represent more than 20% by weight, based on the total weight of
monomers forming the polymer.
8. The polymer according to any one of the preceding claims, in which said nonionic
hydrophobic monomer(s) (b) are chosen from among C1-C8 alkyl acrylates or C1-C8
alkyl methacrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethyl-hexyl
acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and their mixtures.
9. The polymer according to any one of the preceding claims, in which said nonionic
hydrophobic monomer(s) (b) represent from 45% to 75% by weight, in particular from
48% to 68% by weight and more particularly from 50% to 64% by weight, based on the
total weight of monomers forming the polymer.
10. The polymer according to any one of the preceding claims, in which said mixture of
monomers further comprises as cross-linking monomer (c), at least one monomer
different from the compound of formula (I), chosen in the group consisting of
trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate,
ethylene glycol di(meth)acrylate, methylenebisacrylamide, triallylcyanurate,
diallylphtalate, diallylmaleate and their mixtures.
11. The polymer according to any one of the preceding claims, in which said
cross-linking monomer(s) (c) represent less than 5% by weight, based on the total weight
of monomers forming the polymer.
12. The polymer according to claim 4, in which said monomer(s) (d) are of formula (II):
T-A-Z (II)
in which:
- T represents a polymerizable group allowing the copolymerization of the monomer
(d),
- A represents a polymeric chain constituted of:
43
- m units of alkylene oxide of formula -CH2CHR1O- with R1 representing an
alkyl group comprising from 1 to 4 carbons, for example an ethyl or methyl
group, and m varying from 0 to 150,
- p units of alkylene oxide of formula -CH2CHR2O- with R2 representing an
alkyl group comprising from 1 to 4 carbons, for example an ethyl or methyl
group, and p varying from 0 to 150,
- n units of ethylene oxide with n varying from 0 to 150, or from 10 or 15 to
150, or from 10 or 15 to 100, or from 15 to 50, or from 15 to 30,
in which the alkylene oxide units of formula -CH2CHR1O-, the alkylene
oxide units of formula -CH2CHR2O- and the ethylene oxide units are
distributed in blocks, alternating or random and
- Z represents a saturated or unsaturated, linear, branched, cyclic or polycyclic, fatty
chain of at least 10 carbon atoms, optionally comprising one or several heteroatom(s)
such as for example O, S, N or P.
13. The polymer according to claim 4 or 12, in which said monomer(s) (d) represent from 0
to 20% by weight, based on the total weight of monomers forming the polymer.
14. The polymer according to claim 5, in which the additional monomer (e) is chosen from
among:
- 2-acrylamido-2-methylpropanesulfonic acid and its salts,
- the unsaturated telomers of acrylic acid,
- the monomers of formula (e1):
(e1)
in which:
- Ra, Rb and Rc represent, independently of one another, H or CH3 and
- n is an integer equal to 1 or to 2 and
- the monomers of formula (e2):
(e2)
44
in which:
- Ra’, Rb’, Rc’ and Rd’ represent, independently of one another, H or CH3,
- X represents (C=O) or (CH2)r with r=0, 1 or 2,
- (AO) represents a polyalkoxylated chain constituted of alkoxylated units, distributed
in blocks, alternating or random, chosen from among the ethoxylated units EO, the
propoxylated units PO and the butoxylated units BO and
- q is equal to 0 or represents an integer varying from 1 to 150.
15. A method for the preparation, by radical polymerization, of a polymer as defined
according to any one of claims 1 to 14, comprising at least the step consisting of
polymerizing a mixture of:
- at least one anionic monomer (a) having a polymerizable vinyl group,
- at least one nonionic hydrophobic monomer (b) having a polymerizable vinyl group,
- one or several cross-linking monomer(s) (c) including at least one compound of
formula (I):
R
O
O R1 O
(I) n
in which:
- R is a hydrogen atom or a methyl group,
- n is equal to 0 or is an integer from 1 to 30 and
- R1 is a C1-C20 linear or branched alkylene group,
- optionally at least one monomer (d) having a polymerizable vinyl group and an at least C10,
preferably C12 to C36, hydrophobic hydrocarbon chain, which is preferably oxyalkylated,
distinct from the monomer (b) and
- optionally at least one additional monomer (e) that is optionally nonionic, distinct from the
monomer (b).
16. The method according to claim 15, further comprising at least the following subsequent
step:
- polymerization, in the presence of the polymer P1 obtained previously at the end of
the method according to claim 15, of a second mixture of monomers allowing the
obtention of a second polymer P2 comprising:
- at least one anionic monomer (a’) having a polymerizable vinyl group,
45
- at least one nonionic hydrophobic monomer (b’) having a polymerizable vinyl group,
- one or several cross-linking monomer(s) (c’) including at least one compound of
formula (I):
R
O
O R1 O
(I) n
in which:
- R is a hydrogen atom or a methyl group,
- n is equal to 0 or is an integer from 1 to 30 and
- R1 is a C1-C20 linear or branched alkylene group,
- optionally at least one monomer (d’) having a polymerizable vinyl group and an at least C10,
preferably C12 to C36, hydrophobic hydrocarbon chain, which is preferably oxyalkylated,
distinct from the monomer (b’) and
- optionally at least one additional monomer (e’) that is optionally nonionic, distinct from the
monomer (b’).
17. An aqueous composition comprising at least one polymer as defined according to any
one of claims 1 to 14 or as obtained according to the method of claim 15 or 16.
18. A use of a monomer of formula (I):
R
O
O R1 O
(I) n
in which:
- R is a hydrogen atom or a methyl group,
- n is equal to 0 or is an integer from 1 to 30 and
- R1 is a C1-C20 linear or branched alkylene group,
in an amount of less than 5% by weight, based on the total weight of monomers forming
the polymer, for the preparation of a polymer.