1. A water-soluble thickening polyurethane resulting from the condensation: a) of at least one alcohol of formula (I): (I) in which: - x represents 0 or 1, - p and q are integers, at least one of which is non-zero and - 4 < p + x + q < 7, b) of at least one poly(alkylene glycol) and c) of at least one polyisocyanate.

2. The polyurethane according to claim 1, wherein the alcohol a) has a formula (II): (II)

3. The polyurethane according to claim 1, wherein the alcohol a) has a formula (III): (III)

4. The polyurethane according to any one of the preceding claims, resulting from the condensation of: a) 1% to 29% by weight of at least one compound of formula (I), (II) and/or (III), b) 70% to 98% by weight of at least one poly(alkylene glycol) and c) 1% to 29% by weight of at least one polyisocyanate, the sum of these mass percentages being equal to 100%. 26

5. The polyurethane according to any one of the preceding claims, wherein the poly(alkylene glycol) is a poly(ethylene glycol) of which the molecular mass ranges between 2000 g/mol and 20 000 g/mol.

6. An aqueous formulation comprising a polyurethane according to any one of claims 1 to 5.

7. The aqueous formulation according to claim 6, also comprising water and at least one surface-active agent.

8. The aqueous formulation according to claim 6 or 7, also comprising at least one additive selected from the group consisting of a biocide, a solvent, an anti-foaming agent, a pH regulator, a coalescent agent, an encapsulating agent and mixtures thereof.

9. The aqueous formulation according to any one of claims 6 to 8, consisting of: 1) 2% to 50% by weight of at least one polyurethane as claimed in any one of claims 1 to 5, 2) 0.1% to 40% by weight of at least one surface-active agent, 3) 10% to 93% by weight of water, and 4) 0% to 5% by weight of at least one other additive chosen from the group consisting of a biocide, a solvent, an anti-foaming agent, a pH regulator, a coalescent agent, an encapsulating agent and mixtures thereof, the sum of these mass percentages being equal to 100%.

10. The use of a polyurethane according to any one of claims 1 to 5 or of an aqueous formulation as claimed in any one of claims 6 to 9, for thickening an aqueous composition, said composition being selected from the group consisting of a lacquer, a varnish, a paint, a putty, a thick coating, a waterproof coating, an ink, a slurry, a paper coating color, a cosmetic composition and a detergent composition. 27

11. The use according to claim 10, of a polyurethane or of an aqueous polyurethane formulation, as a leveling agent for said aqueous composition.

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
THICKENER FOR AQUEOUS SYSTEMS, FORMULATIONS CONTAINING SAME AND USES
2. APPLICANT(S)
(a) NAME
(b) NATIONALITY
(c) ADDRESS
COATEX
FRENCH Company
35, RUE AMPÈRE,
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
This form is digitally signed
2
The present invention relates to novel associative thickeners belonging to the HEUR
(Hydrophobically modified Ethoxylated Urethane) category. These products contain an
associative compound comprising a carbon-based chain end and a methyl or ethyl branch.
The present invention also relates to intermediate formulations containing such thickeners,
and also to the use of these compounds as thickeners in final compositions, for example paint
compositions.
Paints are made of fillers and pigments and at least one organic polymer called a binder. In
addition to the fillers, pigments and binder, a paint composition also comprises at least one
solvent (which is water in the case of water-phase paints), rheology additives, stability
additives (storage, film formation, UV) and other additives for obtaining specific properties.
The behavior and the properties of paints depend on the nature of their constituents, in
particular of the binder, of the fillers and of the pigments, and also of the rheology additives.
They generally contain one or more thickener(s), the function of which is to control the
rheology of the compositions which contain it (them), both at the stage of their production
and during their conveying, their storage or during their implementation. Given the diversity
of the practical constraints at each of these steps, it is advantageous for the formulator to have
a range of thickeners which exhibit different rheological behaviors when they are used in the
final compositions. In addition, these thickeners can provide the compositions, for example
the paints that contain them, with additional properties.
Among all the paint thickeners, the following are distinguished:
- natural thickeners based on cellulose, also called cellulose ethers, of HEC type or of
HMHEC (Hydrophobically Modified HEC) type,
- acrylic thickeners of non-associative type, called ASE (Alkali Swellable Emulsion) and
those of associative type, called HASE (Hydrophobically modified Alkali Swellable
Emulsion) and
- associative thickening polyurethanes of HEUR (Hydrophobically modified Ethoxylated
URethane) type.
3
Thickening polyurethanes or HEURs result from the condensation between a compound of
poly(alkylene glycol) type, a polyisocyanate and an associative compound of alkyl, aryl or
aryalkyl type made of a hydrophobic end group.
Coatex is responsible for numerous research studies on paint thickeners. Moreover, Coatex
sells the products of the Coapur® range, for example the Coapur® XS products, which are
nonionic thickening polyurethanes providing rheological profiles that vary between the
Newtonian type (high viscosity at high shear gradient) and/or the pseudoplastic type (high
viscosity at low shear gradient).
Document EP 2664640 describes a water-soluble alkoxylated polymer which is nonionic. It is
prepared by reacting a hydrophobic monovalent alcohol, a linear diol compound, a
polyalkylene oxide and a diisocyanate. This polymer is intended to thicken cosmetic
compositions and to make them transparent.
Document WO 2012 096125 also describes a water-soluble alkoxylated polymer. It is
prepared by reacting a polyalkylene oxide, two monovalent hydrophobic alcohols and a
diisocyanate. It is also intended to increase the viscosity of a cosmetic composition.
Document US 2005 187342 relates to thickening agents for aqueous dispersions which are
based on an aqueous preparation of water-dispersible or water-soluble nonionic
polyurethanes. They are obtained from a polyfunctional isocyanate, from a polyether polyol,
from 2-(n-butyl)-1-octanol and from a polyol.
Document US 2008 108775 describes a thickening aqueous composition comprising a watersoluble
or water-dispersible nonionic polyurethane. This polyurethane is obtained by reacting
a hydrophilic polyol comprising ether or ester groups, a hydrophobic compound comprising
at least one saturated or unsaturated, linear or branched hydrocarbon-based chain, and a
diisocyanate.
4
The inventors have developed a novel thickening polyurethane which makes it possible to
very notably increase the viscosity at high shear gradient and to thus confer on the
composition which contains it a good dynamic behavior, that is to say a high viscosity at high
shear gradient. This thickener can be categorized in the category of thickeners of Newtonian
or “ICI builder” type.
A thickener of “ICI builder” type can be defined as a product which results in an increase in
the ICI viscosity when its amount is increased in the paint composition, without significant
increase in the viscosities at low shear rate (Brookfield viscosity).
This novel thickener can, for example, be used alone in a paint composition where it is
required to have a high viscosity at high shear gradient (for example a silk or gloss paint
containing a high binder content).
It can also be used in combination with a thickener of pseudoplastic type. Such a combination
thus makes it possible to obtain a composition which exhibits good dynamic behavior
associated with the presence of the Newtonian thickener and good static behavior associated
with the presence of the thickener of pseudoplastic type.
Such a thickener can be formulated in aqueous phase and, because of its particular structure,
it allows thickening of the final composition without requiring particular equipment or high
shear energy.
This novel thickener has, at the chain ends, hydrophobic groups which result from the
condensation of the alcohol of formula (I):
(I)
5
Document WO 2011/104599 (Coatex) describes rheology modifier polymers for aqueous
systems, in particular paint compositions. The acrylic thickener-type thickeners described can
contain, in particular, ethyl acrylate (EA), methacrylic acid (MAA) and polymerizable
monomeric units of formula:
R – (AO)m – (BO)n – R'
in which:
- R denotes a polymerizable unsaturated group, for example methacrylate,
- A and B denote alkyl groups that are different than one another and have from 2 to
4 carbon atoms, for example ethylene oxide and propylene oxide,
- m and n are integers less than 150, at least one of which is non-zero, and
- R' is made of at least one group of formula below:
CH3 – (CH2)p – CH(-CH3) – (CH2)q –
in which:
• p and q denote integers, at least one of which is non-zero, and
• 5 < p + q < 13.
Such acrylic polymers have a rheological profile different than that of the thickeners of the
present invention. Namely, they fall into the category of acrylic thickeners of pseudoplastic
type (high viscosity at low shear gradient).
DEFINITIONS:
The term “HEUR” is an acronym for “Hydrophobically modified Ethoxylated URethane”.
In the description of the present invention, unless otherwise indicated, the percentages
expressed represent percentages by weight and are expressed relative to the total weight of
the reference element. For example, when it is indicated that a polymer comprises 10% of a
monomer or of a reagent, it is understood that the polymer comprises 10% by weight of this
monomer or reagent relative to the total weight of this polymer.
6
In the description of the present invention, the expression “at least one” denotes one or more
compound(s) (for example one or more alcohol compound(s), one or more poly(alkylene
glycol(s)), one or more polyisocyanate(s)), such as a mixture of 2 to 5 compounds.
The term “formulation” is intended to mean the thickening intermediate entity comprising the
polyurethane agent according to the invention formulated so as to be easier to use in the final
composition to be thickened. For example, the thickening agent according to the invention
can be formulated in the presence of water and of surface-active agents so as to be more
easily pourable and easier to incorporate into the composition to be thickened at ambient
temperature. The viscosity of the formulation before it is incorporated into the final aqueous
composition is, for example, less than 10 000 mPa.s at 25°C and at
100 revolutions per minute.
The term “composition” is intended to mean the final entity to be thickened or that has been
thickened, comprising the polyurethane agent according to the invention, optionally
formulated in the presence, for example, of water and of surface-active agents, and also all of
the constituents thereof, the list of which depends on the final application. For example, the
final composition comprises inorganic pigments and binders, if it is a paint composition.
DETAILED DESCRIPTION OF THE INVENTION:
The polyurethanes of the present invention are thickeners for aqueous compositions, for
example aqueous paint compositions. They make it possible to obtain high viscosities at high
shear gradient and to thus confer good dynamic behavior on the compositions. These
thickening polyurethanes can be categorized in the category of thickeners of Newtonian or
“ICI builder” type.
Some paint compositions, for example silk or gloss paints which contain few pigments
(compared with a matt paint for example) and a lot of binder, must have the highest possible
viscosity at high shear gradient. The term used is Cone Plan viscosity or ICI viscosity,
denoted µI (mPa.s).
7
The thickening polyurethane of the present invention is entirely suitable for aqueous
compositions of this type.
The thickening polyurethane of the present invention can also be used in combination with a
thickener of pseudoplastic type. Such a combination thus makes it possible to obtain a
composition which exhibits good dynamic behavior associated with the presence of the
Newtonian thickener and good static behavior associated with the presence of the thickener
of pseudoplastic type. It is thus possible to adjust the rheological behaviors of the aqueous
formulations at low and high shear gradient.
This novel thickener has specific hydrophobic groups at the chain ends.
HEUR thickener:
A subject of the present invention relates to a thickener belonging to the HEUR
(Hydrophobically modified Ethoxylated URethane) category. It is a nonionic associative
thickening polymer for aqueous compositions.
The thickening polyurethanes or HEURs of the present invention result from the reaction
between a reagent which confers the associativity and which is made of a hydrophobic end
group, a compound of polyol type (for example poly(alkylene glycol)) and a polyisocyanate.
In the context of the present invention, the terms “reaction”, “condensation” and
“polycondensation” are used in an equivalent manner.
More specifically, it is a water-soluble thickening polyurethane resulting from the
condensation:
a) of at least one alcohol of formula (I):
(I)
8
in which:
- x represents 0 or 1,
- p and q are integers, at least one of which is non-zero and
- 4 < p + x + q < 7,
b) of at least one poly(alkylene glycol) and
c) of at least one polyisocyanate.
It is these novel polyurethanes which make it possible, for example, to thicken a paint
composition at high shear gradient (measurement of the ICI viscosity for example).
The polyurethane according to the present invention comprises, as constituent a), a compound
of formula (I). Such a compound is, in the context of the present invention, known as an
“associative compound comprising a carbon-based chain end and a methyl or ethyl branch”.
The expression “x represents 0 or 1” is intended to mean that the branch can be respectively
methyl or ethyl.
Given formula (I), the expression “4 < p + x + q < 7” is intended to mean that the carbonbased
chain comprises between 7 and 10 carbon atoms, for example 7, 8, 9 or 10 carbon
atoms.
Thus, the compounds of formula (I) comprise:
- a carbon-based chain end comprising from 7 to 10 carbon atoms, for example 8
carbon atoms or 9 carbon atoms and
- a -CH3 or -CH2-CH3 branch.
The water-soluble thickening polyurethane can result from the condensation of one or more
alcohol(s) of formula (I).
9
According to one embodiment of the present invention, the polyurethane is made up of
several alcohols of formula (I). According to another embodiment, said polyurethane is made
up of a single alcohol of formula (I).
According to one embodiment of the present invention, the alcohol a) has a formula (II):
(II)
2-octanol
According to this embodiment, the compounds of formula (II) comprise:
- a carbon-based chain end comprising 8 carbon atoms and
- a -CH3 branch (methyl branch).
According to another embodiment of the present invention, the alcohol a) has a formula (III):
(III)
isononanol
According to this embodiment, the compounds of formula (III) comprise:
- a carbon-based chain end comprising 9 carbon atoms and
- a -CH3 branch (methyl branch).
Moreover, the polyurethane comprises, as constituent b), a poly(alkylene glycol).
The term “poly(alkylene glycol)” is intended to mean a polymer of an alkylene glycol derived
from an olefin oxide. The poly(alkylene glycol) chains of the constituent b) according to the
present invention contain a proportion of ethylene-oxy groups, a proportion of propylene-oxy
groups and/or a proportion of butylene-oxy groups. The poly(alkylene glycol) chains
according to the present invention can, for example, comprise a dominant proportion of
ethylene-oxy groups in combination with a secondary proportion of propylene-oxy groups.
Specific examples of alkylene glycol polymers comprise: poly(alkylene glycol)s having an
10
average molecular weight of 1000 g/mol, 4000 g/mol, 6000 g/mol and 10 000 g/mol;
polyethylene polypropylene glycols having a percentage of ethylene oxide of between 20%
and 80% by weight and a percentage of propylene oxide of between 20% and 80% by weight.
According to one aspect of the present invention, the polyurethanes result from the
condensation in particular of a poly(alkylene glycol) which is poly(ethylene glycol). It may
for example be a poly(ethylene glycol) of which the molecular mass ranges between
2000 g/mol and 20 000 g/mol, for example between 8000 g/mol and 15 000 g/mol (limits
included). By way of example, mention may be made of poly(ethylene glycol) (or PEG)
having a molecular mass ranging between 10 000 g/mol and 12 000 g/mol (limits included).
Moreover, the polyurethane comprises, as constituent c), a polyisocyanate.
The term “polyisocyanate” is intended to mean a compound which comprises at least
2 isocyanate functional groups –N=C=O.
According to one aspect of the present invention, the polyurethanes result from the
condensation in particular of a polyisocyanate which is chosen from the group consisting of
toluene diisocyanate, toluene diisocyanate dimers, toluene diisocyanate trimers, 1,4-butane
diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, 1,3-cyclohexane
diisocyanate, 1,4- cyclohexane diisocyanate, 4,4'diisocyanatodicyclohexylmethane, 1-methyl2,4-diisocyanatocyclohexane,
diphenyl methylene diisocyanate (MDI), for example 2,2'-
MDI, 2,4'-MDI, 4n4'-MDI or mixtures thereof, dibenzyl diisocyanate, a mixture of 1-methyl2,4-diisocyanatocyclohexane
and of 1-methyl-2,6-diisocyanatocyclohexane, hexamethylene
diisocyanate biuret, hexamethylene diisocyanate biuret dimers, hexamethylene diisocyanate
biuret trimers, and a mixture of at least two of these compounds.
According to one aspect of the invention, said polyurethane results from the condensation of:
a) 1% to 29% by weight of at least one compound of formula (I), (II) and/or (III),
b) 70% to 98% by weight of at least one poly(alkylene glycol) and
c) 1% to 29% by weight of at least one polyisocyanate,
the sum of these mass percentages being equal to 100%.
11
According to another aspect of the invention, said polyurethane results from the condensation
of:
a) 3% to 10% by weight of at least one compound of formula (I), (II) and/or (III),
b) 80% to 94% by weight of at least one poly(alkylene glycol) and
c) 3% to 10% by weight of at least one polyisocyanate,
the sum of these mass percentages being equal to 100%.
According to one embodiment, the present invention relates to a water-soluble thickening
polyurethane resulting exclusively from the condensation of the following 3 constituents:
a) an alcohol of formula (I):
(I)
in which:
- x represents 0 or 1,
- p and q are integers, at least one of which is non-zero, and
- 4 < p + x + q < 7,
b) a poly(alkylene glycol) and
c) a polyisocyanate.
The production of polyurethanes, which belong to the family of thickeners of HEUR type, is
known to those skilled in the art who will be able to refer to the teaching of the documents
mentioned above in the technological background of the present invention.
Another subject of the present invention also relates to a method for preparing a polyurethane
as described above, said method consisting of a condensation of its various constituents.
12
Formulation of the HEUR thickener:
The polyurethane according to the invention can be formulated or co-formulated with other
constituents or components.
Thus, the present invention also relates to an aqueous formulation comprising a polyurethane
according to the invention, as described above.
This thickening aqueous formulation is intended to be incorporated into a final composition,
for example a paint, a paper coating color or a detergent composition.
The polyurethane according to the invention can be co-formulated in the presence of water.
According to one embodiment, said aqueous formulation according to the invention consists
of:
1) 5% to 50% by weight of at least one polyurethane according to the invention, as
described above and
2) 50% to 95% by weight of water,
the sum of these mass percentages being equal to 100%.
According to another embodiment, said aqueous formulation according to the invention
consists of:
1) 5% to 25% by weight of at least one polyurethane according to the invention, as
described above and
2) 75% to 95% by weight of water,
the sum of these mass percentages being equal to 100%.
The polyurethane according to the invention can be co-formulated in water, in the presence of
at least one surface-active agent. This surface-active agent makes it possible to formulate the
thickener in the form of a less viscous liquid aqueous solution which can thus be more easily
used by the formulator.
13
Thus, according to one embodiment of the present invention, said aqueous formulation
comprises a polyurethane, as described above, and also water and at least one surface-active
agent.
The term “surfactant” or “surface-active agent” is intended to mean a molecule or a polymer
made up of at least one hydrophilic part and of at least one hydrophobic part.
The surface-active agent used in the context of the present invention can be of different
nature, for example it can be anionic or nonionic.
This surface-active agent can be selected from the classes of ionic surface-active agents (in
this case preferably anionic) and/or nonionic surface-active agents and/or mixed surfaceactive
agents (comprising a nonionic and anionic structure in the same molecule). The
preferred surface-active agent is composed of at least one surface-active agent selected from
the class of nonionic surface-active agents, optionally in the presence of an anionic surfaceactive
agent.
Among the suitable anionic surface-active agents, mention may be made of sodium, lithium,
potassium, ammonium or magnesium salts derived from alkyl ether sulfates with alkyl(s)
ranging from C6 to C12, in linear, iso, oxo, geminal, cyclic or aromatic configuration, or C12
alkyl sulfates, alkyl phosphate esters or dialkyl sulfosuccinates. The anionic surface-active
agents are preferably used with at least one nonionic surface-active agent.
As examples of mixed surface-active agents, mention may be made of alkoxylated alkyl
phenol sulfonates. The nonionic surface-active agents can be used alone or in combination
with an anionic surface-active agent. As preferred examples of suitable nonionic surfaceactive
agents, mention may be made of: ethoxylated C4-C18 alcohols (2 to 15 OE),
ethoxylated C4-C18 Guerbet alcohols (2 to 40 OE), ethoxylated C10-C18 monobranched
alcohols (2 to 40 OE), C18 sorbitol esters, ethoxylated sorbitol esters (2 to 20 OE units),
ethoxylated C4-C18 acids (less than 15 OE), ethoxylated castor oil (30 to 40 OE), ethoxylated
hydrogenated castor oil (7 to 60 OE), esters such as glycerol palmitate, glycerol stearate,
ethylene glycol stearate, diethylene glycol stearate, propylene glycol stearate, polyethylene
glycol stearate 200 and ethoxylated C18 esters (2 to 15 OE). The hydrophobic chains can
correspond to linear, iso, oxo, cyclic or aromatic structures.
14
According to one embodiment, the formulation comprises at least one nonionic surface-active
agent optionally combined with at least one anionic surface-active agent, at a total content by
weight ranging from 0.1% to 40% by weight, for example from 5% to 20% by weight or from
10% to 17% by weight. In this case, the weight ratio between the two surface-active agents
can, for example, range between 25/75 and 75/25.
According to one embodiment of the present invention, the polyurethane of the present
invention is formulated in the presence of more than two surface-active agents, for example
three or four.
According to one embodiment, said aqueous formulation according to the invention consists
of:
1) 2% to 50% by weight of at least one polyurethane according to the invention, as
described above, preferably 5% to 30% by weight,
2) 0.1% to 40% by weight of at least one surface-active agent, preferably 2% to 30% by
weight, and
3) 10% to 93% by weight of water, preferably 40% to 85% by weight,
the sum of these mass percentages being equal to 100%.
The polyurethane according to the invention can be formulated in a water-miscible solvent.
The main reason for the addition of an organic co-solvent is to lower the viscosity of this
polyurethane in water, in order to facilitate the handling thereof. The polyurethane is, for
example, formulated with one or more polar solvent(s) belonging in particular to the group
made up of water, methanol, ethanol, propanol, isopropanol, butanols, acetone,
tetrahydrofuran or mixtures thereof.
Two particular examples of water-miscible organic solvents are:
- diethylene glycol monobutyl ether (also known as Butyl CarbitolTM) or ethylene
glycol ether or propylene glycol ether and
- butylene glycol ether.
15
The viscosity of the polyurethane as it is, before it is incorporated into a paint composition
for example, is advantageously less than 10 000 mPa.s at 25°C and at 100 revolutions per
minute, such that it is easier to pour from the storage container and is more rapidly
incorporated into the composition to be thickened at ambient temperature. The water-miscible
solvent chosen for such commercial compositions has, up until now, been exclusively an
organic solvent.
The polyurethane according to the invention can be co-formulated in water, in the presence of
a coalescent agent. In a manner equivalent to a solvent, the coalescent agent makes it possible
to formulate the thickener in the form of a less viscous liquid aqueous solution which can
thus be more easily used by the formulator.
According to one embodiment, said aqueous formulation according to the invention consists
of:
1) 5% to 50% by weight of at least one polyurethane according to the invention, as
described above,
2) 5% to 30% by weight of at least one solvent and/or coalescent agent and
3) 20% to 75% by weight of water,
the sum of these mass percentages being equal to 100%.
According to one aspect of the invention, the aqueous formulation also comprises at least one
additive selected from the group consisting of a biocide, a solvent, an anti-foaming agent, a
pH regulator, a coalescent agent, an encapsulating agent and mixtures thereof.
The term “biocide” is intended to mean a chemical substance intended to destroy, repel or
render harmless pest organisms, to prevent the action thereof or to combat them in any other
ways, by a chemical or biological action.
The term “anti-foaming agent” is intended to mean a substance or a formulation intended to
destroy the air bubbles in a homogeneous or heterogeneous liquid medium (or at its surface)
or to prevent the formation thereof.
16
The term “pH regulator” or “pH-regulating agent” is intended to mean a chemical compound
which makes it possible to adjust the pH to the expected value. For example, the pHregulating
agent can increase the pH; this is the case with the bases such as NaOH.
Alternatively, the pH-regulating agent can decrease the pH; this is the case with acids.
The term “coalescent agent” is intended to mean an agent used in paints, which makes it
possible to lower the Minimum Film Formation Temperature (MFFT) of paint to a
temperature suitable for the desired application conditions (for example, an MFFT of 5°C for
an outside application). By way of examples of coalescent agents according to the invention,
mention may be made of propylene glycol, butyl glycol, 2,2,4-trimethyl-1,3-pentanediol
monoisobutyrate or 2,2,4-trimethyl-1,3-pentanediol diisobutyrate,
2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, and glycol ether derivatives of Dowanol®
type.
The term “encapsulating agent” is intended to mean an agent that creates a hydrophobic
environment, for example a solvation cage. As encapsulating agent, mention is in particular
made of cyclodextrin.
According to one embodiment, said aqueous formulation according to the invention consists
of:
1) 2% to 50% by weight of at least one polyurethane according to the invention, as
described above, preferably 2% to 30% by weight,
2) 0.1% to 40% by weight of at least one surface-active agent, preferably 5% to 30% by
weight,
3) 10% to 93% by weight of water, preferably 40% to 85% by weight, and
4) 0% to 5% by weight of at least one other additive chosen from the group consisting of
a biocide, a solvent, an anti-foaming agent, a pH regulator, a coalescent agent, an
encapsulating agent and mixtures thereof, preferably 0.5% to 4% by weight,
the sum of these mass percentages being equal to 100%.
17
Final aqueous composition and uses of the polyurethane:
A subject of the present invention consists of an aqueous composition comprising a
polyurethane according to the invention or a thickening aqueous formulation according to the
invention, said final aqueous composition being selected from the group consisting of a paint,
a putty, a thick coating, a waterproof coating, a lacquer, a varnish, an ink, a slurry, a paper
coating color, a cosmetic composition and a detergent composition.
Said composition is thickened by means of a polyurethane or of a thickening aqueous
formulation according to the invention.
Moreover, the present invention also relates to the use of a polyurethane according to the
invention or of an aqueous formulation according to the invention, for thickening an aqueous
composition, said composition being selected from the group consisting of a lacquer, a
varnish, a paint, a putty, a thick coating, a waterproof coating, an ink, a slurry, a paper
coating color, a cosmetic composition and a detergent composition.
More specifically, according to one embodiment, the present invention relates to the use of a
polyurethane according to the invention or of an aqueous formulation according to the
invention, for increasing the viscosity of the aqueous composition at high shear gradient.
The expression “increasing the viscosity of the aqueous composition at high shear gradient”
is intended to mean that the viscosity at high shear gradient of the aqueous composition
containing a given amount of polyurethane is greater than that of the same aqueous
composition containing a lower amount of the same polyurethane. In other words, increasing
the amount of polyurethane in the aqueous composition results in increasing the viscosity at
high shear gradient of this composition.
According to one embodiment, the use of a polyurethane according to the invention or of an
aqueous formulation according to the invention makes it possible to selectively increase the
viscosity of the aqueous composition at high shear gradient (for example, ICI viscosity), that
is to say without significant increase in the viscosities at low and medium shear rate (for
example, Brookfield and Stormer viscosities). In other words, increasing the amount of
18
polyurethane in the aqueous composition results in increasing the viscosity at high shear
gradient of this composition, without this increase in amount resulting in significantly
increasing the viscosities at low and medium shear gradient.
The inventors have developed a novel thickening polyurethane which makes it possible to
very notably increase the viscosity at high shear gradient and to thus confer on the
composition which contains it a good dynamic behavior, that is to say a high viscosity at high
shear gradient. This thickener can be categorized in the category of thickeners of Newtonian
or “ICI builder” type.
A thickener of “ICI builder” type can be defined as a product which results in an increase in
the ICI viscosity when its amount is increased in the paint composition, without significant
increase in the viscosities at low and medium shear rate (Brookfield and Stormer viscosities).
This novel thickener can, for example, be used alone in a paint composition where it is
required to have a high viscosity at high shear gradient (for example a silk or gloss paint
containing a high binder content).
According to one embodiment, the aqueous composition to be thickened is of the type of a
gloss paint, a semi-gloss paint, a silk paint or any other paints with a low Pigment Volume
Concentration (PVC).
The “pigment volume concentration” is defined by the following formula:
PVC (%) = 100 x Vc / (Vc+Vl)
with Vc representing the volume of the mineral fillers and
Vl representing the volume of binders in the paint formulation.
According to another embodiment, the aqueous composition to be thickened is of the type of
a paint with a medium or high Pigment Volume Concentration (PVC), which varies between
egg-shell paint and matt paint. In this case, the thickening polyurethane of the present
invention can be combined with another thickener which has a pseudoplastic profile.
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According to one embodiment of the present invention, said polyurethane or said aqueous
polyurethane formulation is used as a leveling agent for said aqueous composition. The
polyurethane according to the invention makes it possible, for example, to increase the
leveling value of the paint which contains it, that is to say the self-smoothing capacity of the
paint during application. This value can, for example, be measured on a contrast chart Leneta,
standard ASTM D4062, called “flow and leveling”.
According to one embodiment of the present invention, the use of said polyurethane or of
said aqueous formulation of polyurethane in an aqueous paint composition makes it possible
in particular to improve the following applicative properties:
- brush drag,
- film build,
- hiding power due to a more even deposition, and
- spatter resistance.
According to one aspect of the present invention, the aqueous composition comprises from
0.02% to 5% by weight of active ingredient of said thickener.
According to another aspect of the present invention, the aqueous formulation comprises
from 0.05% to 2% by weight of active ingredient of said thickener.
The term “weight of active ingredient” is intended to mean the dry weight of polyurethane
according to the invention, independently of the co-formulation ingredients.
According to yet another aspect of the present invention, the aqueous composition comprises
at least one mineral filler selected from the group consisting of calcium carbonate, kaolin, talc
and silicate and/or at least one pigment selected from the group consisting of titanium
dioxide, iron oxide and zinc.
According to one aspect of the invention, the aqueous composition is a paint and comprises at
least one dispersing agent, at least one mineral filler or one mineral pigment, at least one
binder, at least one biocide, at least one anti-foaming agent and optionally one surface-active
agent, a surface agent and/or a coalescent agent, a solvent.
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The examples which follow make it possible to understand the present invention more
clearly, without limiting the scope thereof.
EXAMPLES
The viscosity of the test formulations or of the paint compositions is determined at various
shear rates:
-at low shear rate: the Brookfield viscosity (Bk) which is measured using a Brookfield RVTtype
viscometer, in the unstirred flask, at a temperature of 25°C and at two rotation speeds of
10 and 100 revolutions per minute with the appropriate spindle.
The reading is performed after 1 minute of rotation. Two Brookfield viscosity measurements,
respectively denoted µBk10 and µBk100 (mPa.s), are thus obtained,
- at medium shear rate: the Stormer viscosity, denoted µS (Krebs Units or KU) and
- at high shear rate: the Cone Plan viscosity or ICI viscosity, denoted µI (Poise or P).
Example 1:
This example illustrates the use of a thickener according to the invention in an aqueous silk
paint formulation, without solvent, the make-up of which is given in table 1 below.
It illustrates the thickening capacity of a polyurethane according to the invention
(tests 1-3 and 2-3), using a compound of formula (III). In parallel, this example also
illustrates polyurethanes outside the invention (tests 1-1 and 2-1) and a HASE acrylic
thickener according to (tests 1-2 and 2-2).
Tests 1-1 and 2-1 (outside the invention):
Said polyurethane results from the condensation of, expressed as percentage by weight
relative to the total weight of the polyurethane:
- 2.7% by weight of a non-ethoxylated linear alcohol of formula CH3 – (CH2)7 – OH,
- 92.8% by weight of PEG 10 000 and
- 4.5% by weight of isophorone diisocyanate (IPDI).
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Tests 1-2 and 2-2 (according to the invention):
Said polyurethane results from the condensation of, expressed as percentage by weight
relative to the total weight of the polyurethane:
- 3.5% by weight of a compound of formula (II):
(II)
- 90.5% by weight of PEG 10 000 and
- 6.0% by weight of isophorone diisocyanate (IPDI).
Tests 1-3 and 2-3 (according to the invention):
Said polyurethane results from the condensation of, expressed as percentage by weight
relative to the total weight of the polyurethane:
- 3.4% by weight of a compound of formula (III):
(III)
- 91.3% by weight of PEG 10 000 and
- 5.3% by weight of isophorone diisocyanate (IPDI).
The polyurethanes are formulated in water in the presence of a surface-active agent which is
a C8-C10 fraction of an alkoxylated fatty alcohol (Simulsol®OX1008). The
PU/surfactant/water ratios are 20/5/75.
All the results have been grouped together in tables 2 and 3 below.
For each of the tests, the µBk10, µBk100, µI (in P) and µS (in Krebs Units measured with the
standard module) viscosities were determined, according to the methods described above at T
= 0 and at T = 24 h, at ambient temperature.
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Table 1
Test 1-1 Test 1-2 Test 1-3
OINV INV INV
Amount (% by weight/total formula) 0.88
T = 0
µBk10 2 660 1 730 1 795
µBk100 1 584 957 1 110
µS 95 81 85
µI 2.5 2.2 2.0
T = 24 h
µBk10 3 320 1 730 2 110
µBk100 2 018 1 012 1 333
µS 102 84 91
µI 2.5 2.2 2.0
Table 2
Paint constituent Mass (g)
Water 99.45
Dispersant (Coadis® BR3, Coatex) 3.9
Biocide (Acticide® MBS, Thor) 1.3
Anti-foaming agent (Airex® 901W, Tego) 1.31
NH4OH (28%) 0.5
TiO2 (RHD2® Hunstman) 122.2
CaCO3 (Omyacoat® 850OG, Omya) 84.5
Binder (Acronal 290D, BASF) 270.6
Monopropylene glycol 6.5
Texanol® (Eastman) 6.5
Anti-foaming agent (Tego® 825, Tego) 0.65
PU thickener (according to the tests) Series 1: 28.6
Series 2: variable (see table 3)
Water q.s.f. 650 g in total
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Test 2-1 Test 2-2 Test 2-3
OINV INV INV
Amount (% by weight/total
formula)
1.44 1.44 1.44
T = 0
µBk10 4 560 2 560 2 560
µBk100 2 580 1 360 1 492
µS 118 90 97
µI 3.9 3.9 3
T = 24 h
µBk10 5 800 3 240 3 240
µBk100 3 492 1 872 2 108
µS 126 99 109
µI 4 4 3.2
Table 3
OINV: Outside the INVention INV: According to the INVention
The polyurethanes according to the present invention (tests 1-2, 2-2, tests 1-3 and 2-3) exhibit
a Newtonian-type rheological profile: low viscosity at low and medium shear gradient.
By comparison of the results presented for tests 1-3 and 2-3 (according to the invention), a
significantly improved thickening at high shear rate (µI) is noted in the paint formulation,
whereas the Brookfield and Stormer viscosities change more moderately; this is characteristic
of a Newtonian thickener of “ICI builder” type, which allows a selective increase in the ICI
viscosity as a function of the amount.
The polyurethane of the present invention thus offers a good compromise between Newtonian
behavior (which makes it possible to obtain low viscosities at low shear gradient and medium
shear gradient) and “ICI builder” characteristic which allows a selective increase in the ICI
viscosity as a function of the amount used. The formulator can, thus, adjust the amount of
thickener as a function of the rheological behavior desired at high shear gradient.
The polyurethane outside the invention of test 1-1 makes it possible to obtain a thickening at
high shear rate (µI) of the same order of magnitude as that obtained with the polyurethanes
according to the invention of tests 1-2 and 1-3. Nevertheless, it is noted that the Brookfield
and Stormer viscosities obtained with the polyurethane outside the invention of test 1-1 are
overall higher than those obtained with the polyurethane according to the invention of
tests 1-2 and 1-3 at an identical amount (0.88% by weight relative to the total weight of the
composition).
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The polyurethane of tests 1-1 and 2-1 generates an ICI viscosity that can be modulated as a
function of the amount added to the formula, but it is coupled with viscosities that are too
high at low and medium shear rates. The profile of this polyurethane is not sufficiently
Newtonian.

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WE CLAIM:
1. A water-soluble thickening polyurethane resulting from the condensation:
a) of at least one alcohol of formula (I):

(I)
in which:
- x represents 0 or 1,
- p and q are integers, at least one of which is non-zero and
- 4 < p + x + q < 7,
b) of at least one poly(alkylene glycol) and
c) of at least one polyisocyanate.
2. The polyurethane according to claim 1, wherein the alcohol a) has a formula (II):
(II)
3. The polyurethane according to claim 1, wherein the alcohol a) has a formula (III):
(III)
4. The polyurethane according to any one of the preceding claims, resulting from the
condensation of:
a) 1% to 29% by weight of at least one compound of formula (I), (II) and/or (III),
b) 70% to 98% by weight of at least one poly(alkylene glycol) and
c) 1% to 29% by weight of at least one polyisocyanate,
the sum of these mass percentages being equal to 100%.
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5. The polyurethane according to any one of the preceding claims, wherein the
poly(alkylene glycol) is a poly(ethylene glycol) of which the molecular mass ranges
between 2000 g/mol and 20 000 g/mol.
6. An aqueous formulation comprising a polyurethane according to any one of claims 1
to 5.
7. The aqueous formulation according to claim 6, also comprising water and at least one
surface-active agent.
8. The aqueous formulation according to claim 6 or 7, also comprising at least one
additive selected from the group consisting of a biocide, a solvent, an anti-foaming
agent, a pH regulator, a coalescent agent, an encapsulating agent and mixtures thereof.
9. The aqueous formulation according to any one of claims 6 to 8, consisting of:
1) 2% to 50% by weight of at least one polyurethane as claimed in any one of
claims 1 to 5,
2) 0.1% to 40% by weight of at least one surface-active agent,
3) 10% to 93% by weight of water, and
4) 0% to 5% by weight of at least one other additive chosen from the group
consisting of a biocide, a solvent, an anti-foaming agent, a pH regulator, a
coalescent agent, an encapsulating agent and mixtures thereof,
the sum of these mass percentages being equal to 100%.
10. The use of a polyurethane according to any one of claims 1 to 5 or of an aqueous
formulation as claimed in any one of claims 6 to 9, for thickening an aqueous
composition, said composition being selected from the group consisting of a lacquer,
a varnish, a paint, a putty, a thick coating, a waterproof coating, an ink, a slurry, a
paper coating color, a cosmetic composition and a detergent composition.
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11. The use according to claim 10, of a polyurethane or of an aqueous polyurethane
formulation, as a leveling agent for said aqueous composition.