CYCLOALIPHATIC AND ALIPHATIC DIAMINE-BASED FATTY ACID DIAMIDES USED
AS ORGANOGELATORS
The invention relates first to a fatty acid diamide comprising in its structure both
cycloaliphatic and aliphatic diamines with a specific mole ratio, and to the use of this
product as an organogelling agent or as rheology agent or additive, in particular in
coating, moulding, mastic or sealing, stripping or cosmetic compositions.
US 3 977 894 describes self-activatable rheology additives based on a
homogeneous mixture of organoclays, glyceryl tris(12-hydroxystearate) and a fatty amide
based on a C2 to C18 aliphatic diamine and 12-hydroxystearic acid.
Rheology additives, in particular thixotropic agents based on diamides comprising,
as diamine component, an aliphatic amine and xylylenediamine, and in particular
m-xylylenediamine, are already known with advantageous performance qualities.
However, given the environmental constraints associated with its toxicity and above all its
potential effects on health during its handling, the question of its at least partial
replacement to reduced levels and preferably its total replacement has arisen. Such a
replacement should not, however, significantly affect the rheology performance qualities of
the fatty diamides obtained. More particularly, the target diamides should have high
performance qualities, in terms of thixotropic effect and of sag resistance, with activation
conditions imposed at relatively low temperature, i.e. from 40°C to less than 80°C. This
corresponds in particular to the case of binder compositions in a reactive or non-reactive
organic solvent medium, which solvent should not via an evaporation effect or via a
reaction effect be subjected to high activation temperatures and should not pose a risk to
the environment and health if there is emission of solvent vapours at high temperature nor
a risk to the stability of the binder composition if said solvent is liable to react by heating to
higher temperature. In addition, no significant impairment of the final application
performance qualities should occur. This problem is above all valid for coating
compositions such as paints, varnishes, inks and gel coats, as they are currently known,
or glues or adhesives or stripping or moulding or cosmetic agents in a reactive or non-
reactive organic solvent medium. For example, a non-reactive-type solvent used in paints
is xylene. Examples of reactive solvents (also known as reactive diluents) that may be
mentioned are styrene or acrylic monomers in gel coat or moulding compositions based
on unsaturated polyesters or vinyl esters.
The affinity of m-xylylenediamine and of diamides based on this diamine and
12-hydroxystearic acid relative to the solvents used in the application compositions, in
particular in coatings or glues or adhesives, makes this diamine an essential component
for, organogelling additivesv or rheology additives, suitable for these applications. More

particularly, in coatings such as paints, varnishes and inks in a non-reactive solvent
medium, such as xylene, the question of its replacement demands the search for a good
compromise of performance qualities in this solvent and with the organic binders that may
be used in this medium, and without significantly affecting the rheology performance
qualities during the final application.
Depending on the parameters associated with the working medium, parameters
associated with the specific composition (molecular and structural parameters) and other
parameters associated with the activation conditions in a given system, the rheological
performance qualities may vary significantly and it is very difficult to extrapolate and to
predict these performance qualities in general from what is known for performance
qualities of a very particular known system. The effect of gelation in a particular target
application medium necessitates a specific compromise between the capacity of the
amide to be solubilized (with a specifically limited target solubility) and associated with the
capacity to form crystalline fibres and the tendency towards precipitation and
sedimentation in said medium based on said organic solvent. The term "solvent" in the
definitions given above and below should be understood as a main organic solvent that
cannot be subjected to (is not capable of) activation at high temperature, in particular
above 90°C. Consequently, said solvent according to the invention is capable of being
activated only at temperatures below 90°C.
Thus, the aim of the present invention is to overcome the outlined drawbacks and
is therefore directed towards developing novel fatty diamides of specific and selective
composition. This composition comprises diamines of cycloaliphatic structure in partial
replacement and more particularly in total replacement for xylylenediamines, in particular
for m-xylylenediamine in the presence of at least one aliphatjc diamine as essential amine
components of said diamides in specific ratios. The invention is thus directed towards
organogelling agent performance qualities that are satisfactory and in particular at least as
good as those of organogelling agents based on xylylenediamine alone (100% of the
amine component), i.e. without any replacement with said cyclic diamine, taken as
comparison reference. The diamides according to the invention are particularly capable of
being activated at low temperature as described above.
The advantages of the present invention, relative to the products and uses of the
prior art in the field of binder compositions in organic solvent medium, are rheological
performance qualities that are satisfactory and preferably at least as good as those
obtained with amides based on m-xylylenediamine alone (in the total absence of
cycloaliphatic diamine) with at least equivalent performance qualities. These performance

qualities are obtained without having the environmental and health constraints associated
with the toxicity of said aromatic diamine.
The present invention first covers said diamide of specific composition.
The second subject of the invention concerns the use of said diamide as an
organogelling agent.
Another subject is the organogelling agent comprising said diamide.
Finally, the invention relates to a binder composition comprising said diamide for
various uses.
Thus, the first subject of the invention relates to a characterized fatty acid diamide
which comprises at least one reaction product obtained from a reaction mixture
comprising:
a) at least one cycloaliphatic diamine comprising a ring of 6 carbon atoms and in
particular globally comprising, including said ring, from 6 to 18 carbon atoms, said
diamine preferably being chosen from: 1,3-bis(aminomethyl)cyclohexane
(1,3-BAC), 1,4-bis(aminomethyl)cyclohexane (1,4-BAC), 1,2-bis-
(aminomethyl)cyclohexane (1,2-BAC) and isomer mixtures thereof,
decahydronaphthalenediamines, isophoronediamines, more preferentially 1,3-bis-
(aminomethyl)cyclohexane (1,3-BAC), 1,4-bis(aminomethyl)cyclohexane
(1,4-BAC), and even more preferentially 1,3-bis(aminomethyl)cyclohexane
(1,3-BAC),
b) a fatty hydroxy acid chosen from 12-hydroxystearic acid (12-HSA),
9-hydroxystearic acid (9-HSA), 10-hydroxystearic acid (10-HSA), 14-
hydroxyeicosanoic acid (14-HEA) or binary or ternary or quaternary mixtures
thereof, preferably 12-hydroxystearic acid or a binary or ternary mixture of 12-
hydroxystearic acid with the other hydroxy acids mentioned,
c) at least a second diamine selected from linear primary aliphatic C2 to C-12,
preferably C2 to C8 and more preferentially C2 to C6 diamines,
d) optionally, at least one monoacid selected from saturated and non-hydroxylated
linear C6 to C18, preferably C6 to C15 and more preferentially C6 to C12 carboxylic
acids,
e) optionally, at least a third primary diamine different from c) selected from linear
aliphatic C2 to C12, preferably C2 to C8 and more preferentially C2 to C6 diamines,
f) at least one aromatic diamine chosen from xylylenediamines, preferably from m-,
p-xylylenediamines (m-, p-XDA), more preferentially m-xylylenediamine (m-XDA),
said aromatic diamine possibly being partially or totally replaced with a
cycloaliphatic diamine as defined in point a).

According to a preferred option, the molar percentage of a/(a+f) is at least 50%
and ranges up to 100% and the molar percentage of (a+f) / (a+c+e+f) which represents
the mole ratio of the cycloaliphatic amine a) and aromatic amine f) relative to all of the
amines, ranges from 30% to 80% and preferably from 30% to 65%. More particularly, the
mole ratio a/(c+e) of the diamine a) to the other aliphatic diamines is at least 0.25 and
preferably ranges from 0.45 to 0.95 and more preferentially from 0.5 to 0.85.
The term "linear" has a meaning, relative to a branched structure, only for chains
comprising at least 4 carbon atoms and means for these chains the absence of any
branching, chains of shorter length (C2 and C3) being by definition always linear.
According to another possibility of the present invention, said cycloaliphatic
diamine a), preferably 1,3-BAC or 1,4-BAC, is in the presence of xylylenediamines f),
preferably p-XDA or m-XDA, more preferentially m-XDA, with said diamine a) representing
from 50 mol% to 99 mol% of the total number of moles of diamine a) + xylylenediamines
f), preferably from 60% to 99% of said total number.
According to an alternative and more preferred option of the invention, said
diamine f) is absent (0%) with a mole ratio a/(a+f) of 100%, preferably with said
cycloaliphatic diamine a) being 1,4-BAC or 1,3-BAC. Said diamine a) may be present
alone or in the form of a mixture comprising said diamine a).
According to a more particular option, said diamide according to the invention
comprises:
i) a diamide consisting of the product of reaction of 1 mol of said diamine a) with
2 mol of said hydroxy acid b) as defined above, preferably said hydroxy acid b)
being the 12-hydroxystearic acid, and
ii) a diamide consisting of the product of reaction of 1 mol of diamine c) with 2 mol of
said hydroxy acid b) as defined above, preferably said hydroxy acid b) being the
12-hydroxystearic acid, and
iii) a diamide consisting of the product of reaction of 1 mol of diamine according to e)
and of 2 mol of said hydroxy acid b) as defined above, preferably said hydroxy
acid b) being the 12-hydroxystearic acid.
The diamide of the invention may comprise at least 2 and preferably at least 3
different reaction products as derived from the reaction between said diamines a), c) and
e) and optionally xylylenediamines f) and monoacids b) and optionally d).
According to a particular mode, said monoacid d) is present in a proportion such
that the mole ratio d/(b+d) is less than 0.5 and preferably ranges between 0.02 and 0.5.
According to a particular preference, said diamide of the invention is in the form of

less than 20 u and more preferentially less than 15 (j. The determination of said size may
be performed with measuring apparatus equipped with a laser detector.
The micronization is performed by mechanical milling optionally followed by
screening or by air jet milling to obtain the finest powders with a controlled and narrower
particle size distribution.
The second subject of the invention concerns the use of the diamide of the
invention as an organogelling agent in organic solvent medium.
Thus, said additive may be used as a rheology additive, in particular in the form of
a preactivated paste preconcentrated in an organic solvent. The organic solvent may be a
mixture of solvents. Preferably, it is a polar solvent or comprises at least one polar
solvent. A preferred important use of said diamide is a use (as rheology additive) in a
coating composition in particular in paints, varnishes, inks and gel coats or in a glue and
adhesive or stripping or moulding or cosmetic composition. More preferentially, said use
concerns a coating composition, taking into account the questions posed by affinity in
these media of the m-xylylenediamine to be replaced according to the object of the
invention, as explained above.
Another subject of the invention is an organogelling agent, in particular rheology
additive which comprises at least one diamideas defined according to the invention, as
described above. More particularly, it may be a rheology agent or additive, in particular a
thixotropic agent in a composition preconcentrated in at least one organic solvent,
including a mixture of solvents, preferably in at least one polar organic solvent, in the form
of a preactivated paste.
The term "polar organic solvent" according to the above description includes in
its definition or should be interpreted as meaning "at least one polar organic solvent" or
"a mixture of organic solvents comprising at least one polar organic solvent". A solvent
considered as being a polar organic solvent is a solvent comprising at least one polar
group, for instance an alcohol or ester group. As examples of polar organic solvents
according to the first interpretation option, mention may be made of ah alcohol such as
ethanol or butanol or a mixture thereof and, according to the second interpretation
option (mixture of organic solvents comprising at least one polar organic solvent), a
mixture of such an alcohol (ethanol or butanol) with a non-polar solvent, for instance
xylene.
Finally, the invention covers an organic binder composition, which comprises, as
rheology agent (or additive being a term equivalent to agent), at least one diamide as
defined above according to the invention.

More particularly, this organic binder composition is a coating, paint, varnish, ink or
gel coat composition or a glue.or adhesive composition or stripping or moulding or
cosmetic composition. According to a more preferred option, said composition is a coating •
composition. According to another possibility, said composition is a mastic or sealing
composition. According to another option, this composition is a moulding composition.
Moulding or gel coat or radiation-crosslinkable coating compositions are compositions in
reactive solvent medium (also known as reactive diluent), such as unsaturated polyesters
or vinyl esters in styrene or in another equivalent comonomer or multifunctional acrylic
(meaning acryl) monomers and/or oligomers, said oligomers using as reactive diluent a
multifunctional acrylic monomer.
More specifically, said organic binder may be selected from: epoxy resins,
unsaturated polyesters, vinyl esters, alkyds, silane resins, polyurethanes, polyester
amides, solvent-based (non-reactive diluent) acrylic resins, acrylic (multifunctional)
monomers and/or oligomers with, in the latter case, the reactive diluent being an acrylic
(multifunctional) monomer or chlorinated elastomers and non-chlorinated elastomers and
chlorinated polymers other than chlorinated elastomers, preferably epoxy resins,
unsaturated polyesters, vinyl esters, alkyds, polyurethanes, polyester amides, solvent-
based acrylic resins and said acrylic monomers and/or oligomers or chlorinated
elastomers and non-chlorinated elastomers.
Acrylic monomers and/or oligomers mean monomers and/or oligomers bearing at
least one acrylate or methacrylate function and in particular multifunctional, i.e. with at
least two of said acrylate or methacrylate functions per molecule.
The examples presented below are given as illustrations of the invention and of its
performance qualities and do not in any way limit its scope.



II - Methods and tests used
The formulations are evaluated with two tests: the flow (sag) resistance test and an
evaluation of the viscosity at various speeds.
Flow resistance test
This is performed using a sag controller (Levelling/Sagging Tester from Sheen
Instruments) which makes it possible to establish the resistance of a coating to sagging
due to gravity. This controller, made of stainless steel and fitted with a flat blade,
comprises notches of increasing value

The test consists in depositing various strips of paint of parallel thickness onto a
contrast card by means of the sag controller. The contrast card is immediately placed
vertically, with the thinnest film at the top. The thickness at which the strips merge
indicates the tendency towards sagging.
Viscosity evaluation
This is performed using a Brookfield® RV viscometer at 25°C (spindle: S 4). The
spindle speed is set at 50 rpm (rotations per minute) and the viscosity of each paint after it
has stabilized is measured. The operation is repeated for speeds of 20 rpm, 10 rpm,
5 rpm and 1 rpm.
Ill - Preparation and characterization of the diamides (or organogelling agents,
rheoloqv additives)
EXAMPLE 1: Amide based on meta-xylylenediamine and hexamethylenediamine and
12-HSA
61.29 g of meta-xylylenediamine (0.46 mol), 63.8 g of ethylenediamine (i.e.
0.54 mol) and 315.2 g of 12-hydroxystearic acid (1.00 mol) are placed in a 1 litre round-
bottomed flask equipped with a thermometer, Dean-Stark apparatus, a condenser and a
stirrer, under a stream of nitrogen.
The mixture is heated to 200°C, still under a stream of nitrogen. The water
removed begins to accumulate in the Dean Stark apparatus from 150°C. The reaction is.
monitored by the acid number and the amine number. When the acid and amine values
are less than 10 (in mg KOH/g), the reaction mixture is cooled to 150°C and then emptied
into a silicone mould. Once it has cooled to room temperature, the product is micronized
mechanically by milling and screened to obtain a fine and controlled particle size with a
mean size obtained of 7 µm.
For EXAMPLES 2, 3 and 4: the same procedure was used, but with the
proportions of reaction components presented in Table 2 below:



IV- Evaluation of the rheoloqical performance qualities in a paint formulation
The amides prepared were evaluated in (reactive) epoxy paint formulations with a
high solids content (or high dry extract) in xylene.
1) Preparation of the paint formulations
A formulation known as "millbase" is prepared with the proportions presented in
Table 3 below and in the following manner:
The following and successive operations are performed in a dispersing bowl
(Dispermill® 2075 yellow line, supplier: Erichsen) heated via a jacket system:
1.1) Introduction of the epoxy binders and of the dispersant and the degassing agent.
Homogenization is performed for 2 minutes at 800 revolutions/minute (800 rotations per
minute or 800 rpm).
1.2) Introduction of the fillers and pigments, followed by milling at 3000 rpm for 30 minutes
using a 7 cm paddle. The jacketed bowl allows this step to take place at room temperature
with a bath of cold water (at 20°C).
1.3) Introduction of the solvents (butanol according to Table 3) and homogenization.
2) Activation of the amide additive in the "millbase"
24 hours after preparation of the millbase, the formulation is again dispersed using
a 4 cm paddle at 3000 rpm. The diamide to be evaluated is introduced into the millbase
and activated in situ at two tested activation temperatures, 50°C and 70°C, for 20 minutes
and at 3000 rpm.
The evaluation is not performed until 24 hours after the activation and 30 minutes

paints thus obtained are adjusted as regards their paint application viscosity, with a
xylene/butanol mixture (1/1 by weight) to about 0.4 P or about 40 mPa.s (more precisely
to 0.37-0.38 P or 37-38 mPa.s) measured on cone 4 at 25°C at 2500 s-1 using a
Brookfield® CAP 1000 viscometer. The proportions between the hardener and the solvent
mixture are defined in Table 4 below. The amount of 1/1 xylene/butanol mixture used for
the viscosity adjustment may vary, but in general by less than 1% (variation) from one test
to another.
After the adjustment, the paint is mixed/homogenized at 1500 rpm for 2 minutes
and then left to stand for 30 minutes before evaluation 24 hours later.


3) Evaluation of the rheology of the prepared formulations of the epoxy paints and
results
Various paint formulations were prepared with the prepared amides 1 to 4
according to the proportions shown in Tables 3 and 4 and with two activation
temperatures examined, 50 and 70°C, according to the protocol outlined above.
The sag resistance and rheology results show that amide 3 based on 1,3-bis-
(aminomethyl)cyclohexane has a thixotropic effect comparable or at least similar to that of
amide 1 based on m-xylylenediamine for the same formulation activated at 50°C or at
70°C.
The sag resistance and rheology results show that amide 4 based on 1,3-
bis(aminomethyl)cyclohexane has a thixotropic effect comparable or at least similar to that
of amide 2 based on m-xylylenediamine for the same formulation activated at 50°C or at
70°C.
Consequently, amides 3 and 4 based on 1,3-bis(aminomethyl)cyclohexane have
the necessary and very satisfactory characteristics of a rheology additive. The diamine
1,3-bis(aminomethyl)cyclohexane can therefore replace m-xylylenediamine in the context
of the invention with results that are at least as good as those obtained without
replacement, but, in the latter case, with the toxicity problem of said diamine not solved
and drawbacks mentioned.
The sag resistance results are presented in Table 5 and the rheological
performance results are presented in Table 6 below.


The Theological evaluation results (viscosity and thixotropic index Tl 1/10 and Tl
5/50) are presented in Table 6 below.


CLAIMS
1. Fatty acid diamide, characterized in that it comprises at least one reaction product
obtained from a reaction mixture comprising:
a) at least one cycloaliphatic diamine comprising a ring of 6 carbon atoms and in
particular globally comprising, including said ring, from 6 to 18 carbon atoms, said
diamine preferably being chosen from: 1,3-bis(aminomethyl)cyclohexane (1,3-
BAC), 1,4-bis(aminomethyl)cyclohexane (1,4-BAC), 1,2-bis-
(aminomethyl)cyclohexane (1,2-BAC) and isomer mixtures thereof,
decahydronaphthalenediamines, isophoronediamines, more preferentially 1,3-
bis(aminomethyl)cyclohexane (1,3-BAC), 1,4-bis(aminomethyl)cyclohexane (1,4-
BAC) and even more preferentially 1,3-bis(aminomethyl)cyclohexane (1,3-BAC),
b) a fatty hydroxy acid chosen from 12-hydroxystearic acid (12-HSA),
9-hydroxystearic acid (9-HSA), 10-hydroxystearic acid (10-HSA), 14-
hydroxyeicosanoic acid (14-HEA) or binary or ternary or quaternary mixtures
thereof, preferably 12-hydroxystearic acid or a binary or ternary mixture of 12-
hydroxystearic acid with the other hydroxy acids mentioned,
c) at least a second diamine selected from linear primary aliphatic C2 to C12,
preferably C2 to C8 and more preferentially C2 to C6 diamines,
d) optionally, at least one monoacid selected from saturated and non-hydroxylated
linear C6 to C18, preferably C6 to C15 and more preferentially C6 to C12 carboxylic
acids,
e) optionally, at least a third primary diamine different from c) selected from linear
aliphatic C2 to C12, preferably C2 to C8 and more preferentially C2 to C6 diamines,
f) at least one aromatic diamine chosen from xylylenediamines, preferably from m-,
p-xylylenediamines (m-, p-XDA), more preferentially m-xylylenediamine (m-XDA),
said aromatic diamine possibly being partially or totally replaced with a
cycloaliphatic diamine as defined in point a).

2. Diamide according to Claim 1, characterized in that the molar percentage of a/(a+f)
is at least 50% and ranges up to 100% and in that the molar percentage of (a+f)/(a+c+e+f)
ranges from 30% to 80% and preferably from 30% to 65%.
3. Fatty acid diamide according to Claim 1 or 2, characterized in that said
cycloaliphatic diamine a), preferably 1,3-BAC or 1,4-BAC, is in the presence of
xylylenediamines f), preferably p-XDA or m-XDA and more preferentially m-XDA and in
that said diamine a) represents from 50 mol% to 99 mol% of the total number of moles of
diamines a) + xylylenediamine f).

4. Fatty acid diamide according to Claim 1 or 2, characterized in that said diamine f)
is absent, with a mole ratio a/(a+f) of 100%, preferably with said cycloaliphatic diamine a)
being 1,4-BAC or 1,3-BAC.
5. Diamide according to one of Claims 1 to 4, characterized in that it comprises:
i) a diamide consisting of the product of reaction of 1 mol of said diamine a) with 2
mol of said hydroxy acid b) as defined according to Claim 1, preferably said
hydroxy acid b) being the 12-hydroxystearic acid, and
ii) a diamide consisting of the product of reaction of 1 mol of diamine c) with 2 mol of
hydroxy acid b) as defined according to Claim 1, preferably said hydroxy acid b)
being the 12-hydroxystearic acid, and
iii) a diamide consisting of the product of reaction of 1 mol of diamine according to e)
and of 2 mol of hydroxy acid b) as defined according to Claim 1, preferably said
hydroxy acid b) being the 12-hydroxystearic acid.
6. Diamide according to one of Claims 1 to 5, characterized in that it comprises at
least 2 and preferably at least 3 different reaction products as derived from the reaction
between said diamines a), c) and e) and optionally the xylylenediamines f) and the
monoacids b) and optionally d).
7. Diamide according to one of Claims 1 to 6, characterized in that said monoacid d)
is present in a proportion such that the mole ratio d/(b+d) is less than 0.5 and preferably
ranges between 0.02 and 0.5.
8. Diamide according to one of Claims 1 to 7, characterized in that it is in the form of
a micronized powder, preferably in the form of a powder with a mean size by volume of
less than 20 µ and more preferentially less than 15 µ.
9. Use of the diamide as defined according to one of Claims 1 to 8 as an
organogelling agent in an organic solvent medium.
10. Use according to Claim 9, characterized in that said diamide is used as a rheology
additive, in particular in the form of a preactivated paste preconcentrated in an organic
solvent.
11. Use according to Claim 9 or 10, characterized in that said diamide is used in a
coating composition, in particular in paints, varnishes, inks and gel coats or in a glue or
adhesive composition or stripping or moulding or cosmetic composition, more particularly
in a coating composition.
12. Use according to Claim 9 or 10, characterized in that said diamide is used in a
mastic or sealing composition.
13. Organogelling agent, in particular a rheology additive, characterized in that it
comprises atleast one diamide as defined according to one of Claims 1 to 8.

14. Organic binder composition, characterized in that it comprises as rheoiogy additive
at least one diamide as defined according to one of Claims 1 to 8.
15. Organic binder composition according to Claim 14, characterized in that it is a
coating composition, in particular a paint, varnish, ink or gel coat composition or a glue or
adhesive or stripping or cosmetic composition.
16. Organic binder composition according to Claim 14, characterized in that this is a
mastic or sealing composition.
17. Organic binder composition according to Claim 14, characterized in that this is a
moulding composition.
18. Composition according to Claim 14, characterized in that said binder is selected
from: epoxy resins, unsaturated polyesters, vinyl esters, alkyds, silane resins,
polyurethanes, polyester amides, solvent-based acrylic resins, acrylic monomers and/or
oligomers or chlorinated elastomers or non-chlorinated elastomers and chlorinated
polymers other than chlorinated elastomers.