POLYESTER RESINS BASED ON FATTY ACIDS WITH A SHORT OIL LENGTH,
AQUEOUS DISPERSIONS AND ASSOCL\TED COATINGS
The invention relates to a fatty acid-based polyester -resin, in particular an alkyd
resin, with a short or even zero oil length, modified to a high proportion by rosin or
5 derivatives thereof, a binder composition based on this modified resin, more particularly an
aqueous dispersion based on this resin with no presence of organic solvent, and to
applications as binder in coatings and in particular in water-based coatings for adhesives,
paints, surface coatings, primers or varnishes. This polyester resin, and in particular alkyd
resin, uses a high content of starting materials of renewable origin and has specific
10 performance qualities, in particular concerning the development of hardness over time after
application and the reduction of yellowing. In particular, the novel resin may be used as
binder in decorative or industrial water-based coating compositions capable of curing in air
with or without siccativating agent.
Alkyds in organic solvent medium, also referred to as being solvent-based, are
15 resins that have been known for a long time to those skilled in the art, and are used in
general in decorative and industrial paint formulations and coatings. To satisfy questions as
regards comfort of use, odor and toxicity, specific alkyd emulsions have been developed
and marketed for about 20 years, with advantageous performance levels in terms of gloss,
drying, appearance/color, stability and odor. A technical solution for conventional
20 implementation, employed to form alkyd emulsions that are stable over time, consists in
using a combination of a nonionic surfactant with an anionic surfactant as described in WO
2008/076360.
Despite these improvements, certain parameters and performance levels still remain
to be improved, such as the resistance to yellowing, the blocking resistance, the hardness,
25 the water sensitivity and the biodegradability. The tendency toward yellowing is a natural
and intrinsic property of alkyd resins, which thus limits their use to quite specific end uses,
for instance primers, surface coatings, woods and trims. The first alkyd emulsions
described in the literature concern alkyds with large oil lengths of about 65% to 82% as
described in Colloids Surfaces A. Physicochem. Eng. Aspects 1995, 94, 161-171. The
30 emulsification of resins with a smaller oil length is relatively difficult to perform, due to
the lower affinity of surfactants with the resin, as explained in Prog. Org. Coat. 1994, 24,
281-97. Nevertheless, nowadays, commercial products have an average oil length of 50%,
as described in WO 2009/140192 or even a smaller oil length up to approximately 40% for
- 2 -
the lowest oil lengths, as described in Prog. Org. Coat. 2000, 40, 253-266 or even more
recently in WO 2008/076360, For a more systematic and universal use, it is necessary to
find solutions that guarantee products which develop less yellowing for applications of
wider scope such as on walls or ceilings. Nowadays, these applications are almost
5 exclusively reserved for acrylic emulsions, which have been known for a long time for
their good resistance to yellowing and to oxidation, but acrylic emulsions have drawbacks
such as lower gloss," water sensitivity (lower water resistance) and poorer chemical
resistance.
The resin of the present invention proposes to overcome the mentioned drawbacks
10 of the prior art, while at the same time affording high dispersibility in water without any
need for organic solvent and in the absence of groups that make the resin self-dispersing.
This capacity makes it possible to obtain resin dispersions without any organic solvent or
protective colloids and which are stable on storage, and to obtain coatings associated with
high gloss and high hardness, and, by virtue of its hydrophobic nature, high water
15 resistance, such as high resistance to yellowing over time. An additional advantage during
the drying of the resin dispersions according to the present invention is the faster
development over time of high, stable hardness, this being achieved without the need for
systematic addition of a siccativating agent of cobalt type. This therefore leads to an
amicable solution for man and for his environment due to the absence of organic solvents
20 in the dispersion and also the absence of siccativating agents on drying, but also via the
choice of the essential raw materials, insofar as a large proportion of these raw materials is
of renewable and durable origin and may also lead to chemical structures that are more
readily biodegradable. The dispersions of the invention and the coatings resulting
therefrom are thus favorable toward environmental protection, while at the same time
25 having application qualities that are at the very least identical, if not improved, with respect
to conventional water-based coatings. In addition to the envirormiental protection, the
highly renewable nature of said aqueous binders according to the present invention should
be underlined, which binders are predominantly prepared from rosin and natural fatty
substances. This advantage is appreciable since, in certain cases, the proportion of .
30 renewable raw materials reaches a level of 100% on the overall composition of the resin
(surfactants excluded). This enables the manufacture of this novel type of resin, which may
be used as binder, by virtue especially of the durable and seasonal availability of said raw
materials. These same reasons also make it possible to limit the environmental impact via a
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reduced carbon imprint and an improved life cycle. These two parameters reflect the
impact of the manufactured products on the environment and health. "Renewable" or "biosourced"
resources in particular make it possible to reduce the emissions of greenhouse
gases such as carbon dioxide.
5 With this aim, the present invention proposes a novel range of polyester resins
based on oxidizable and/or non-oxidizable fatty acids, in particular alkyd resins, with a
greatly reduced or zero short oil length, for their dispersion in water with the aid of
surfactants, and which are capable of substantially curing without the excessive supply of
unsaturated fatty oils or acids. These dispersions, which are commonly known as
10 "emulsions", give, after application to a substrate, coatings that are stable over time and
ensure low yellowing evolution and also substantial development of hardness after
application and drying, despite having a greatly reduced or zero oil length. The very r
capacity of certain resins with a very small oil length, in particular from 0 to 15%, to cure
strongly and rapidly with the drying time, and above all without the necessary supply of
15 siccativating agent, is a significant advantage in the current environmental context. More
particularly, in this context, the use of cobalt-free drying systems is an increasingly
important need, given the increasing environmental restrictions on the use of cobah as a
siccativating agent.
More particularly, the resin according to the invention with a zero oil length (0%)
20 or an oil length ranging up to 5% (meaning an oil length ranging from 0 to 5%), in addition
to its capacity to be used as a resin for obtaining aqueous dispersions for water-based
coatings, as described above, also has the capacity to be used as a binder resin for nonwater-
based coatings and more particularly for two-pack applications, for example as
"coil" coating resins for application to metal sheets. The same performance improvements
25 as with water-based coatings are obtained, especially in terms of hardness and chemical
resistance, for example. The non-water-based coatings obtained with a binder resin
according to the invention, having a zero oil length (0%) or an oil length ranging up to 5%,
give in addition (additional performance) a significant improvement in the adherence to
steel and in particular to galvanized steel.
30 Alkyds are oligomers that are conventionally obtained by polycondensation
between diacids and polyols in the presence of a more or less large proportion of "oil" or of
"oxidizable unsaturated fatty acids". The diacids and polyols usually used to form the
polymer structure are phthalic anhydride, isophthalic acid, pentaerythritol and glycerine (or
»
- 4 -
glycerol). The number-average molecular masses Mn may thus range between 1000 and
10 000 g/mol, as a function of the OH/CO2H (hydroxy/carboxy) ratio used. Monoacids
such as benzoic acid and rosin (mainly and predominantly containing natural resinous
acids such as abietic acids including dehydroabietic acid, pimaric acids, mercusic acids and
5 communic acids) may be added to the alkyds as acid component. These components thus
make it possible to reduce the oil length and to increase the hardness of the alkyd. On the
other hand, reducing the oil length makes the resin less readily dispersible in water with
surfactants and above all without the aid of solvent. According to Paintindia, Nov. 2007,
61-65, it is essential to use organic solvent in order to facilitate the dispersion in water, but
10 the presence of such an organic solvent is incompatible with environmental protection as
demanded in the present invention. By reducing the oil length of certain alkyds, we have
found, unexpectedly, that the rosin used under the conditions of the invention considerably
facilitates the development over time of the hardness of the coatings, in particular alkyd
coatings, thus formed during oxidative drying also known as siccativation and also
15 facilitates the aqueous dispersion of the resin without any need for organic solvent or
protective colloid. The hardness associated with the observed curing of the resin increases
over time after application of the coating composition and offers an excellent final
hardness to the film, which is markedly superior to those recorded for conventional alkyd
emulsions, with oil lengths usually of between 40% and 85%.
20 The invention relates firstly to a polyester resin based on fatty acids, which is short
in oil or of zero oil length, modified with rosin and/or derivatives thereof These resins
may be used as organic binders in aqueous dispersion for water-based coatings. More
particularly, the resin with a zero oil length (0%) or with an oil length ranging up to 5%
may also be used as organic binder for two-pack (2K) non-water-based coatings, in
25 particular for "coil" or metal sheet and preferably for galvanized steel.
Next, the invention relates to an organic binder composition comprising at least one
modified resin as described above and more particularly comprising, in addition to this
modified resin, at least one second resin different from the first one and selected from
polyesters based on fatty acids.
30 The third subject of the invention concerns an aqueous dispersion of resin
comprising at least one modified resin as defined according to the first subject of the
invention or at least one organic binder composition as defined according to the second
subject of the invention.
4
- 5 -
Another subject of the invention concerns a process for preparing an aqueous
dispersion, as defined according to the third subject of the invention.
The invention also covers a coating composition which comprises at least one
modified resin as defined according to the first subject of the invention or at least one
5 organic binder composition as defined according to the second subject of the invention or
at least one aqueous dispersion as defined according to the third subject of the invention.
The invention also relates to the use of the modified resins according to the first
subject or of the organic binder compositions according to the second subject or of the
aqueous dispersions according to the third subject of the invention, as binder in coating
10 compositions.
Finally, the invention relates to the use of the modified resins according to the first
subject with a zero oil length or with an oil length ranging up to 5%, as organic binder in
non-water-based coatings based on a two-pack reactive system, more particularly for "coil"
applications on metal sheets.
15 Thus, the first subject of the invention relates to a polyester resin, in particular an
alkyd resin, which resin:
is based on at least one fatty acid
has a zero oil length (0%) or an oil length between 0 and 35%, preferably greater
than 0 and up to 25%, more preferentially up to 15%
20 - has a weight ratio of oxidizable fatty acids (monoacids) relative to the overall fatty
acids of 0 or more than 0 and ranging up to 1
is based on an acid component comprising, in addition to said fatty acid, from 30%)
to 85%, preferably from 35% to 75%, more preferentially from 40% to 75% and
even more preferentially from 45% to 75%) by weight, relative to the total weight of
25 said resin, of rosin and/or rosin derivatives bearing at least one carboxylic acid
function, and more particularly for its maleinized derivatives (maleinized rosin
derivatives), bearing from 3 to 4 carboxylic fijnctions.
According to a preferred embodiment, the resin of the invention comprises less than
5%, preferably less than 3% by weight and more preferentially no (0%) aromatic
30 compound, for instance of phthalic type (phthalic, isophthalic, trimellitic or terephthalic
acid or anhydride), besides the rosin derivatives that may be used. The term "rosin
derivatives" means natural derivatives such as dehydroabietic acid.
-6-
The resin of the invention is, according to another preferred case, based on an acid
component comprising, in addition to said fatty acid, in addition to said rosm and/or in
addition to said rosin derivatives, at least one acid compound containing at least one
carboxylic acid function and having an overall fiinctionality of 2 to 3, the overall
5 functionality including the acid function and another possible function, said compound
being chosen from: saturated polyacids or ethylenically unsaturated polyacids or hydroxy
acids. The saturated polyacids have no ethylenic unsaturation that is reactive during their
use and may very well be derived from unsaturated polyacids, containing at least one
reactive unsaturation, by hydrogenation of these unsaturated polyacids. More particularly,
10 the resin of the invention may be based on an acid component which comprises at least two
from among said acid compounds, with at least one chosen from saturated polyacids and
another chosen from unsaturated polyacids, this being in addition to said fatty acid and said
rosin and/or said rosin derivatives. As saturated polyacid that is suitable for use according
to the invention, the choice may be made from the acid and/or the anhydride corresponding
15 to: succinic acid of functionality 2, adipic acid of functionality 2, sebacic acid of
functionality 2, dodecanedioic acid of functionality 2, citric acid of functionality 3, the C36
fatty acid dimer of functionality 2 to 2.2 or the C54 fatty acid trimer of functionality 2.5 to
3. As unsaturated polyacid that is suitable for use, the choice may be made from the
existing acid and/or anhydride corresponding to: itaconic acid of functionality 2, maleic or
20 fumaric acid of functionality 2 or tetrahydrophthalic acid (THP) of functionality 2. Among
the preferred polyacids, mention may be made of polyacids comprising at least one C36
fatty acid dimer and/or C54 fatty acid trimer. As defined above, said acid compound,
containing at least one carboxylic function and having an overall functionality of 2 to 3,
may also be chosen from hydroxy acids that may thus be present in said acid component in
25 addition to the fatty acids and the rosin and derivatives thereof As preferred hydroxy acids
that may thus be present, mention may be made of glycolic acid or lactic acid.
A combination of several polyacids and monoacids is often used in order to
optimize the physicochemical properties of the resin, in particular of the alkyd, and more
particularly to obtain the desired hardness/suppleness compromise. The incorporation into
30 the resins according to the invention, in particular into the alkyds, of aromatic acid
derivatives such as phthalic derivatives (diacid/anhydride) or benzoic derivatives
(monoacid) is possible, but preferably with a content of less than 5% by weight and more
preferentially with less than 3% by weight. Even more preferentially, there is no aromatic
- 7 -
derivative (0% aromatics) besides any possible natural rosin derivatives as described
above. The presence of a monoacid component such as abietic or pimaric acids, in
particular of rosin and/or derivatives thereof, and more particularly in such a high
proportion, constitutes the essential element of the invention for enabling the particular
5 properties observed. The rosin content is high and ranges from 30% to 85%, preferably
from 35% to 75%, more preferentially from 40% to 75% and even more preferentially
from 45% to 75%. The fatty acids used, given their natural origin, are mixtures comprising
saturated fatty acids, unsaturated fatty acids containing non-conjugated unsaturations and
unsaturated fatty acids containing conjugated unsaturations. These fatty acids, and also
10 fatty acid dimers and/or trimers synthesized from these same natural fatty acids, afford the
suppleness and flexibility necessary for the binder and the coating obtained which results
therefrom.
The term "fatty acid" defined in the broadest sense means a C12 to C54 carboxylic
acid.
15 The term "oil length", as used in the present invention, means the weight
percentage, relative to the total weight of the resin, of the weight of "fatty monoacids" or of
oils or stand oil derivatives (stand oil is a product resulting from the reaction at high
temperature, 250-300°C, of a mixture of oil and fatty acid), this weight percentage being
expressed as a weight equivalent of triglyceride derivatives (oils) which correspond to the
20 fatty acids, said fatty acids being "oxidizable". Any calculation or mention of this
characteristic in the present invention is based on this defmition. The term "oxidizable fatty
acids" means, according to the present invention, fatty acids or derivatives (oils or stand
oils) with an iodine number of greater than or equal to 80 mg of iodine per g of product.
Said monoacids or triglycerides (oils) may be mixtures of natural origin, comprising up to
25 30% by weight of saturated fatty acids.
Preferably, the proportion of oxidizable (air-reactive) unsaturation in the resin of
the invention is zero (0) or is greater than 0 and ranges up to 0.25 and preferably up to 0.15
mmol of oxidizable double bonds per gram of dry resin (undiluted).
According to a particular possibility, the resin of the invention is based on an
30 alcohol component comprising at least one polyol of fimctionality ranging from 2 to 10 and
preferably from 3 to 6. The polyols that are suitable for use according to the invention may
be selected from: ethylene glycol, polyethylene glycol, preferably with a number-average
molecular mass Mn ranging from 300 to 6000, propylene glycol (1,2-propanediol), 1,3-
1
-8-
propanediol, dipropylene glycol, triethylene glycol, glycerol, diglycerol,
trimethylolpropane or trimethylolethane, pentaerythritol, dipentaerythritol, sorbitol,
mannitol, methyl glucoside, polyglycerol, in particular glycerol oligomers, such as
Polyglycerol-3 (glycerol trimer) and decaglycerol and, preferably, glycerol oligomers and
5 mixtures thereof, such as Polyglycerol-3, which Polyglycerol-3 is a mixture of glycerol
oligomers (glycerol oligomerized in the presence of oligomers containing 30% to 55% by
weight of glycerol trimer constituting the predominant oligomer), this product being sold
by Solvay. The polyol that is most preferred is polyglycerol-3 which is oligomerized and -
has a molecular mass markedly greater than that of glycerol, with a functionality ranging
10 from 5 to 6. By virtue of its higher molecular mass and of its high fimctionality, this polyol
makes it possible more readily to increase the final molecular mass of the resin, in
particular of the alkyd resin, while at the same time ensuring a narrower molecular
distribution.
The preferred resin of the invention has an acid number of less than 8 and a
15 number-average molecular mass Mn ranging from 1000 to 10 000 g/mol, measured by
GPC in THF and expressed as polystyrene equivalents.
The Tg of the resin of the invention measured by DSC, after two passages at a
temperature sweep speed of 10°C/min, may range from -40 to 50°C and preferably from
-20 to 35°C.
20 More particularly, according to a first version, the resin has an oil length that is
between 0 and 35%, and is preferably greater than 0 and ranges up to 25% and more
preferentially up to 15%, with presence of at least one oxidizable fatty acid (monoacid).
This means that the resin comprises an air-oxidizable structure. According to a more
particular case of this oxidizable resin version, the content of oxidizable unsaturation in
25 said resin is greater than 0 and may range up to 0.25 and preferably up to 0.15 mmol of
oxidizable double bonds per gram of dry resin. In such a case (resin of oxidizable
structure), said fatty acid is selected from fatty monoacids of plant or animal origin
preferably of Ci6 to C24, with a mean iodine number ranging from 100 to 200.
According to the given definition of the invention, the fatty acid may be an
30 oxidizable fatty acid (fatty monoacid) or a non-oxidizable fatty acid, in particular a
polyacid such as fatty acid oligomers and in particular C36 and C54 fatty acid dimers and/or
trimers, respectively. Said fatty acid may be oxidizable and selected from fatty acids of
soybean oil, sunflower oil, tall oil (TOPA), castor oil, dehydrated castor oil, linseed oil or
t <
-9-
rapeseed oil, said fatty acids being used as such or in the form of corresponding oils
(triglyceride esters) of fatty acids or in the form of corresponding stand oils of fatty acid .
oils. Said stand oils, which are well known to those skilled in the art, are in fact derivatives
of fatty acid oils obtained at high temperature by standolization of these oils. These cases
5 of fatty acids or of fatty acid oils have oxidizable unsaturations as defined above according
to the iodine number characteristic of greater than or equal to 80 mg of iodine per gram of
produced acid or oil or stand oil of fatty acid oil.
According to a preferred version of the resin of the invention, it is based on a
polyacid comprising at least one C36 fatty acid dimer and/or C54 fatty acid trimer and based
10 on a polyol comprising at least one glycerol and/or pentaerythritol and/or dipentaerythritol
oligomer, preferably a mixture of glycerol oligomers comprising the glycerol trimer, more
particularly polyglycerol-3.
According to a more particular version, the polyester resin of the invention is an
alkyd resin, with an oil content (oil length) of greater than 0%, preferably ranging up to
15 25%andmorepreferentialIy up to 15%.
Another category of resin according to the invention has a zero oil length or oil
content (0%) and is commonly referred to as being "oil-free", with said fatty acid being
selected from non-oxidizable fatty acids and thus with a corresponding content of
oxidizable unsaturation that is 0 mmol per gram of dry resin. In this case, said fatty acid is
20 preferably selected from saturated fatty acids (including fatty acids that are initially
oxidizable, which have been hydrogenated and consequently become non-oxidizable) or
from fatty acid oligomers, preferably C36 dimers (including hydrogenated dimers) and/or
C54 trimers (including hydrogenated trimers). Preferably, such a resin (0% oil) is based on
an alcohol component comprising as polyol a glycerol oligomer, preferably a mixture of
25 glycerol oligomers, and more preferentially polyglycerol-3, and, as fatty acid, a C36 fatty
acid dimer and/or a C54 fatty acid trimer (hydrogenated or non-hydrogenated). A resin with
comparable behavior, in particular for applications in a two-pack coating system, is also a
resin with an oil content ranging up to 5%, which, in addition to said fatty acid selected
from the non-oxidizable fatty acids as defined above, comprises (in addition) minor weight
30 proportions of an oxidizable fatty acid leading to said oil proportion ranging up to 5%. Said
oxidizable fatty acid, which is minor in the latter case, may be present as residual acid with
the rosin used: for example, "tall oil" rosin comprises small proportions (about 4%) of tall
oil fatty acid, which is oxidizable. Thus, as in this particular case, said oxidizable acid may
-10-
also be present or added in such minor proportions to arrive at an oil length that may be up
to 25%.
The preparation of said resin according to the invention, in particular the alkyd, is
performed by polycondensation reaction under an inert atmosphere at standard
5 temperatures of between 180°C and 300°C, preferably between 250°C and 270°C, and
more preferentially with application of a vacuum (reduced pressure) of moderate level
ranging from 50 to 250 mmHg, at the end of the polycondensation in order to reduce the
reaction times. It is possible, in order to prevent and/or fiirther reduce the coloration and
oxidation of the rosin during the synthesis, to use additives, in particular antioxidants, as
10 employed in the preparation of rosin esters used in particular for adhesives: phenol sulfites,
paraformaldehyde, hypophosphorous acid, trialkyl or triphenyl phosphites. A more
exhaustive list of additives that may be used for this purpose is described in US 4 744 925,
column 2, lines 50-62, which list is incorporated herein by reference.
The second subject of the invention is thus an organic binder composition which
15 comprises at least one resin as defined above according to the invention.
According to a more preferred case, this composition comprises at least two resins
and, more precisely, in addition to the first resin as defined according to the invention
above, it comprises at least one second resin different from the first, and with this second
resin being selected from resins of polyesters based on fatty acids, preferably from
20 modified alkyd resins. Thus, preferably, said polyesters based on fatty acids are chemically
modified alkyds chosen from: silicone alkyds, urethane alkyds, alkyd-acrylic hybrids.
These binder compositions may be used as such or in the. preparation of the aqueous
>
dispersions of resins of the invention, for water-based coatings.
According'to a particular variant of this organic binder composition, which is well
25 suited to non-water-based or solvent-based coatings and more particularly for two-pack
(2K) reactive systems, even more particularly for "coil" coatings on metal sheets, said first
resin is a resin according to the invention and has a zero oil length (0%) or an oil length
ranging up to 5%.
The third subject of the invention is an aqueous dispersion of resin which comprises
30 at least one resin or at least one binder composition as defined above according to the
present invention. According to a particular preferred variant of this aqueous dispersion
according to the invention, it comprises, in addition to said resin or said binder
composition, both as defined according to the invention described above, at least one
-11-
surfactant selected from: at least one anionic surfactant and at least one nonionic surfactant
or at least one surfactant of mixed structure and with an overall weight content relative to
said resin ranging from 2% to 15% and preferably from 5% to 10%. According to the
present invention, a surfactant of mixed structure is a surfactant which comprises both a
5 nonionic structure, such as a polyoxyalkylene segment (more particularly oxyethylene
and/or oxypropylene units) and an anionic structure (for instance a sulfonate or sulfate or
phosphate or phosphinate group) on the same molecule or molecular chain. Examples of
such surfactants that may be mentioned include sulfonate or sulfate or, phosphate
phosphinate esters of polyether alcohols or of alkoxylated fatty alcohols, with nonionic
10 structures (polyether) and anionic structures (sulfate, sulfonate or phosphate or
phosphinate), combined on the same molecule.
The dispersion according to the invention may have a solids content ranging from
30% to 70%) and preferably from 40%) to 60%) and a mean particle size ranging from 100 to
500 rm:. The preferred dispersion according to the invention is free of any organic solvent,
15 this meaning, according to the present invention, a corresponding content of volatile
organic compounds (VOC) in said dispersion of less than 1000 ppm, preferably less than
500 ppm and more preferentially less than 100 ppm.
Even more particularly, the aqueous dispersion of resin according to the present
invention is a mixture of, or comprises as a mixture, a first aqueous dispersion of resin as
20 defined according to the invention as described above and at least one second dispersion of
resin, which second dispersion is different from the first dispersion, this second dispersion
of resin being selected from dispersions of alkyds, which are optionally modified, or
acrylic, including styrene-acrylic, dispersions (or emulsions), or dispersions of other
polymers and in particular dispersions of saturated or unsaturated polyesters, or
25 polyurethanes. According to this particular case of aqueous dispersion, the weight content
of said first dispersion ranges from 50% to 99.5%). Said modified alkyd dispersions that
may be suitable for said second dispersion, according to this particular case, are chosen
from alkyd dispersions modified with acrylic, styrene, styrene-acrylic, vinyl, silicone or
urethane. Said second dispersion is also selected so as to be compatible with the first
30 aqueous dispersion as defined according to this particular dispersion case and, more
particularly, it is based on a resin or a polymer that is compatible with the resin of the
present invention, which resin has as specificity a greatly reduced or zero oil length.
-12-
A fourth subject of the invention concerns a process for preparing said aqueous
dispersion, which process comprises a step of emulsification at a temperature of from 30 to
90°C and preferably from 50 to 85°C of at least one resin and/or of at least one organic
binder composition, the resin and the binder composition as defined above according to the
5 invention, by phase inversion in a reactor stirred via a dual-flow stirring system.
In point of fact, the resins, after the final polycondensation phase, are cooled to
120-180°C and are then transferred into an emulsifier in order to be dispersed therem in
water in the presence of surfactants. The emulsion is preferably obtained via the phase
inversion technique using a reactor stirred via a dual-flow system at a temperature of
10 between 30°C and 90°C and preferably at 50-85°C. The direct emulsification technique is
incompatible with this type of resin. The temperature imposed during the phase inversion
is adjusted as a function of the intrinsic viscosity at elevated temperature of the alkyd or
polyester resin. The resin is emulsified, at neutral or slightly alkaline pH, via more or less
partial neutralization of the residual carboxylic functions, according to a standard process
15 combining a surfactant or, preferably, a mixture of ionic (anionic) surfactant and of
nonionic surfactant. For these two types of process, at least one surfactant is used. This
surfactant is selected from ionic, preferably anionic, and/or nonionic and/or hybrid
surfactants of mixed structure (comprising in the same molecule a nonionic structure such
as an ethoxylated and/or propoxylated structure and an anionic structure). The presence of
20 surfactants improves the stability of the dispersion, thus preventing sedimentation and/or
coalescence during the hot forming process and during the storage/use of the product. A
selection criterion for the nonionic surfactants used is the HLB index (hydrophiliclipophilic
balance) representing the ratio of hydrophilic and hydrophobic characters in the
surfactant. Preferably, a combination of a nonionic surfactant and of an anionic surfactant
25 is preferred to obtain stable dispersions with a small particle size, preferably less than 300
rmi. Among the anionic surfactants that are suitable for this invention, mention may be
made of sodium, lithium, potassium, ammonium or magnesium salts, alkyl ether sulfates
with alkyl ranging from Cg to Ci8 or C12 alkyl benzene sulfates or alkyl sulfates, alkyl
phosphate or dialkyl sulfosuccinate esters or even soaps obtained from the corresponding
30 fatty acids. The anionic surfactants are preferably used with at least one nonionic
surfactant. Examples of mixed surfactants (nonionic + anionic mixed structure) include
alkoxylated alkyl phenol sulfonates or phosphonates. The nonionic surfactants may be used
alone, but, preferably, they are in combination with an anionic surfactant. As preferred
1
- 1 3 -
examples of suitable nonionic surfactants, mention may be made of: ethoxylated C12-C18
fatty alcohols (6 to 50 OE), ethoxylated iso Cio fatty alcohols (6 to 50 OE), ethoxylated
mono-branched Cio-Cis fatty alcohols (6 to 50 OE), sorbitol fatty esters, ethoxylated
sorbitol esters (5-50 OE), alkyl polyglucosides, glucamides, glycerol, diglycerol or
5 polyglycerol fatty esters, ethoxylated fatty acids (7-100 OE), ethoxylated castor oil
(hydrogenated or non-hydrogenated) (30-40 OE), glycol or polyethylene glycol fatty acids,
nonionic polymers and other block copolymers, for instance poly(propylene glycol)-
poly(ethylene glycol) block copolymer. Th? preferred aqueous dispersion comprises at
least one nonionic surfactant optionally combined with at least one anionic surfactant in an
10 overall (nonionic plus anionic) weight content relative to the alkyd or polyester resin of
from 2% to 15%, preferably from 5% to 10%, and with a preferred ionic to nonionic
weight ratio ranging from 25/75 to 50/50 in the case of a nonionic and anionic
combination. The pH of the medium is preferably adjusted as a function of the acidity of
the resin. This is why a basic aqueous solution, of from 1% to 50% and preferably from
15 10% to 20% by weight of base, is initially introduced after the addition of the surfactants,
at the emulsification temperature (cf table 4). To this end, basic (alkaline) aqueous
solutions are used starting with LiOH, NaOH, KOH, aqueous ammonia or amines,
preferably tertiary or hindered amines that are more or less hydrophilic, such as
diethanolamine, triethanolamine, aminomethylpropane or triethylamine.
20 The aqueous dispersion of the resin may also be obtained by self-emulsification of
the resin without surfactant, for a resin with an acid number of at least 40 mg KOH/g, after
at least partial neutralization of the carboxylic functions of the resin. However, in the
context of the present invention, it is preferable for the acid number to be < 8 in order to
have the best water resistance for the resulting final coating.
25 The aqueous dispersion according to the invention is preferably fi-ee of any
protective colloid.
The dry extracts or solids contents of said dispersions of the invention range from
30%) to 70%, preferably from 40% to 60% and more preferentially from 40%> to 55%o.
Another subject of the invention relates to a coating composition which comprises
30 as binder at least one resin or at least one binder composition or at least one aqueous
dispersion, with said resin or binder composition or aqueous dispersion being as defined
above according to the invention. According to a more particular and preferred case, said
composition is a water-based coating composition. Said coating is preferably selected from
(
-14-
decorative or industrial coatings, and in particular, for industrial coatings, chosen from
anticorrosion coatings, and preferably from water-based coatings for adhesives, paints,
surface, coatings, primers and varnishes. The preferred coating is selected from decorative
or industrial water-based varnishes or paints. These water-based coating compositions and
5 in particular pauits and varnishes have the additional advantage of drying without
mandatorily supplying (or at a reduced level) a siccativating agent.
The coating composition based on aqueous dispersions may also comprise a
siccativating agent, which may be present in a reduced or zero content (normal), and in this
case said resin used as binder preferably has an oil length ranging up to 25% and
10 preferably from 15% to 25%. Given their appropriate molecular masses and oil length, said
resins in particular with an oil content ranging from 15% to 25%, under the effect of a
siccativating agent such as cobalt, allow, in addition to high hardness and great resistance
to yellowing, excellent blocking resistance, with no point of attachment or of peeling
observed in a test, after drying for 24 hours at room temperature and 24 hours of contact.
15 Such blocking resistance performance is expected only for certain acrylic dispersions, but
is entirely exceptional for polyester dispersions, in particular alkyd dispersions, as
described in the present invention.
Moreover, the presence of hydroxyl functions in the resins defined according to the
invention makes it possible to produce, for applications termed industrial, crosslinks by
20 means of a second component (two-pack system known as 2K) such as isocyanates
(blocked or non-blocked) or melamines to form films with a higher molecular weight
leading to superior mechanical or chemical properties: chemical resistance and mechanical
strength such as increased longevity and durability.
The coating composition according to the present invention also covers a coating
25 composition which comprises as binder at least one resin as defined above according to the
invention and having a zero oil length (0%) or a resin having an oil length ranging up to
5% as defined above or at least one binder composition based on such a resin (zero oil
length or oil length ranging up to 5% as defined above). This particular coating
composition more particularly concerns an anticorrosion protective coating of great
30 chemical resistance for coil applications. More particularly, such a coating composition
may be used in a two-pack (2K) reactive system.
A penultimate subject of the invention relates to the use of at least one resin or of at
least one binder composition or of at least one aqueous dispersion, as defined above
(
-15-
according to the invention, as binders in coatings. More particularly, this use relates to
decorative or industrial water-based coatings selected from adhesives, paints, surface
coatings, primers or varnishes. These coatings are suitable for substrates selected from:
wood, metals, plaster, concrete, composites or plastics, plastics such as silicone,
5 polyethylene, PVC, polycarbonate, polypropylene or polystyrene.
A more particular use concerns resin with a zero oil length or with an oil length
ranging up to 5%, as defined above according to the invention or the corresponding binder
composition or aqueous dispersion (comprising said resin), this use being as a binder for
two-pack (2K) reactive systems in coil coatings, for marine applications or as anticorrosion
10 for protecting metals (metal surfaces).
Moreover, the high hydrophobicity and the excellent adhesion, which are qualities
afforded by said resins in aqueous dispersion according to the present invention, make it a
preferred binder that may be used equally well in coatings in aqueous and non-aqueous
medium for preventing the corrosion of metal surfaces. Among the other substrates
15 selected, wood may also be found, it being noted that the hydrophobic nature and the
presence of "rosin" units derived from the wood, offer excellent properties of adhesion to
wood. Surprisingly, we have also found, by chance, that these binders also had high
properties of adhesion to plastics such as silicone, polyethylene, ABS, polycarbonate or
PVC, or to plaster, ceramic, brick or composite materials. The coating compositions
20 formulated with at least one aqueous dispersion of said resin may contain a significantly
reduced or even zero content of at least one siccativating agent. Preferably, these
compositions may be free of siccativating agents and in particular free of cobalt as
siccativating agent. Similarly, by virtue of its high potential for physical drying, slightly
larger coating thicknesses would be allowed for equivalent drying times, thus increasing
25 the productivity and also improving the conditions and working intervals (shortened
interval) for the handling and use of coated pieces, after coating.
The final subject of this invention relates to substrates coated with at least one
(substrate) coating, obtained from at least one resin or from at least one binder composition
or from at least one aqueous dispersion of resin or from at least one coating composition
30 derived fi"om said resin, as defined above according to the present invention. In certain
applications with a high concentration of fillers and in a two-pack system, supplying a
siccativating agent based on cobalt, manganese, lead, vanadium, calcium, barium,
strontium, cerium, zinc and iron is unnecessary. Already, given the physical drying
- 1 6 -
performance demonstrated by the compositions based on resin of reduced oil length, in
particular from 0 to 15%, the presence of siccativating agent is in no way essential with
such a coating composition.
5 EXPERIMENTAL SECTION
By way of illustration of the invention, the following examples describe, without
any limitation on the claimed subjects, the synthesis of said resins for binders, in particular
water-based, and the performance of the dispersions and of the coatings thus obtained. An
illustration of the performance in a two-pack (2K) system is also presented at the end of the
10 experimental section.
1) Raw materials used (see Table 1 below)
Table 1: Raw materials used for the preparation of the tested resins
Acid or
Iodine hydroxyl
Commercial name
Supplier Chemical name Function number number
or product type
(mg h/g) (mg
KOH/g)
Nouracid® SZ35 Oleon Soybean fatty acid Fatty acid 120-150 195-205
SYLFAT®2 Arizona Tall oil fatty acid Fatty acid 155 194
^ Croda
Pripol 1009 Fatty acid dimer Polyacid / 195-205
Mixture of fatty acid
(J) Croda
PripollOiy dimers and trimers Polyacid / 195-210
(75/25)
Itaconic acid Acros Orgaiucs Itaconic acid Polyacid / 860
Rosin of Chinese Pine oil rosin, with a
TER-HELL &
Pinus massoniana content of resinous acids Rosin / 165-175
CO GMBH
type -90%
Tall oil rosin, resinous
FOR85 Forchem Rosin / 165-175
acids: >85%
rr J 1® T-vm- Hydrogenatedrosin „ . , ,,.
Hydrogral DRT Resinous acids:-89% ''°^'" ' ^^^
Succinic acid Aldrich Succinic acid Polyacid / 950
Sebacic acid Aldrich Sebacic acid Polyacid • / 550
Poly glycerol (mixture of
1000-
Polyglycerol-3 Solvay oligomers, centered on Polyol /
1200
35-55% trimers)
»
- 1 7 -
Pentaerythritol Perstorp Pentaerythyitol Polyol / 1645
Glycerol Cargill 1,2,3-Propanetriol Polyol / 1828
4,4'-Thiobis(3-methyl-6-
AOX-R Alladchem tert-butylphenol) Antioxidant
(CAS 96-69-5)
Ammonium Anionic
Zephrym®3300 CRODA
dodecylbenzenesulfonate surfactant
Propylene oxide/ethylene Nonionic
Atlas® G5000 CRODA
oxide block copolymer surfactant
Short-oil (37%) alkyd
resin as a dispersion in Reference
Synaqua® 4804* Cray Valley
water (solids content: resin
50%)
Synolac® 9605 S „ ^ ,. Polyester resin for general Reference
65 "coil" application resin
BORCHI® OXY- OMG- Iron complex dissolved in Siccativating
COAT BORCHERS propylene glycol agent
Cobalt complex dissolved
DURHAM® ROCKWOOD in a dearomatized Siccativating
COBALT lOWM PIGMENTS hydrocarbon-based agent
solvent .
Aqueous solution of
. ^ „ „ , ^ „ ® , . ^ _ THOR methylisothlazoline n- j
ACTICIDE^MBS -^trcn^Tc /A^T'r\ A e Biocide
CHEMIE (MIT) and of
benzisothiazolinone (BIT)
DISPERBYK® ^^°^^ copolymers
. . . BYK CHEMIE containing groups with Dispersant
high affinity for pigments
BYK® 022 BYK CHEMIE Polysiloxane base Antifoam
antifoam
TIONA® 595 /-^T /-^D A T Titanium dioxide Pigment
AQUAFLOW® AQUALON- Hydrophobically - ~ ;
NMS450 HERCULES modified polyacetal Thickener
polyether
AQUAFLOW® AQUALON- Modified polyacetal . ,
NHS 300 I HERCULES | polyether | ^M^^ener j |
* Symbolized as SA4804 in figures 1 and 2
- 1 8 -
2) Preparation of the starting resins
13 resins were prepared according to the corresponding procedures described below
in Examples 1 to 13.
5 Example 1
185.2 g of Pripol® 1009, 1453.3 g of pine oil rosin, 6 g of AOX-R (phenol sulfite)
and 185.2 g of polyglycerol-3 are placed in a stirred, temperature-regulated 5-liter reactor,
under a nitrogen atmosphere. The mixture is heated to 250-270°C and the water of
condensation is removed until an acid number of 6 mg KOH/g is obtained.
10
Example 2
The same procedure as for Example 1 is used with the following products and
amounts: 592.0 g of Pripol® 1009, 1034.0 g of pine oil rosin, 6 g of AOX-R (phenol
sulfite) and 374.0 g of polyglycerol-3. The water of condensation is removed until an acid
15 number of 4 mg KOH/g is obtained.
Example 3
The same procedure as for Example 1 is used, but with the following products and
amounts: 6.5 g of soybean fatty acid Nouracid® SZ35, 71.4 g of pine oil rosin and 22.0 g of
20 polyglycerol-3. The water of condensation is removed until an acid number of 4 mg
KOH/g is obtained.
Example 4
85.0 g of tall oil fatty acid, 837.0 g of tall oil rosin (For 85), 84.0 g of succinic acid
25 and 264.9 g of polyglycerol-3 are placed in a stirred, temperature-regulated 2-liter reactor,
under a nitrogen atmosphere. The mixture is heated to 250-270°C and the water of
condensation is removed until an acid number of less than 6 mg KOH/g is obtained.
Example 5
30 The same procedure as for Example 4 is used, but starting with the following
amounts: 9.3 g of soybean fatty acid, 64.2 g of pine oil rosin, 5.2 g of succinic acid and "
22.0 g of polyglycerol-3. The mixture is heated to 250-270°C and the water of
condensation is removed until an acid number of less than 4 mg KOH/g is obtained.
-19-
Example 6
9.5 g of soybean fatty acid, 65.6 g of pine oil rosin and 21.2 g of polyglycerol-3 are
placed in a stirred, temperature-regulated 0.25 liter reactor, under a nitrogen atmosphere.
5 The mixture is heated to 250-270T and the water of condensation is removed until an acid
number of less than 2-3 mg KOH/g is obtained. Next, 3.25 g of itaconic acid are added at
150°C and the mixture is heated at 180°C until a final acid number of 8 mg KOH/g is
obtained.
10 Example 7
139.6 g of soybean fatty acid Nouracid® SZ35, 868.2 g of pine oil rosin, 83.6 g of
succinic acid, 68.1 g of sebacic acid and 340.5 g of polyglycerol-3 are placed in a stirred
reactor as in Example 4. The mixture is heated to 250-270°C and the water of condensation
is removed until an acid number of less than 6 mg KOH/g is obtained.
15
Example 8
116.5 g of soybean fatty acid Nouracid® SZ35, 801.5 g of tall oil rosin, 67.6 g of
succinic acid and 264.9 g of polyglycerol-3 are placed in a stirred reactor as in Example 4.
The mixture is heated to 250-270°C and the water of condensation is removed until an acid
20 number of less than 7 mg KOH/g is obtained. 16.5 g of succinic acid are then added and
the condensation is continued until an acid number of 5.5 mg KOH/g is obtained.
Example 9
180.0 g of SYLFAT® 2 (tall oil fatty acid), 770.0 g of pine oil rosin, 69.0 g of
25 succinic acid and 273.9 g of polyglycerol-3 are placed in a stirred reactor as in Example 4.
The mixture is heated to 250-270°C and the water of condensation is removed until an acid
number of less than 7 mg KOH/g is obtained. Next, 22.8 g of succinic acid are added and
the condensation is continued until an acid number of 4 mg KOH/g is obtained.
Example 10
30 220.0 g of SYLFAT® 2 (tall oil fatty acid), 664.0 g of pine oil rosin, 73.6 g of
succinic acid, 255.9 g of Pripol 1017 (75/25 fatty acid dimer/trimer mixture) and 255.9 g
of polyglycerol-3 are placed in a stirred reactor as in Example 4. The mixture is heated to
1 t
-20-
250-270°C and the water of condensation is removed until an acid number of less than 5
mg KOH/g is obtained.
Example 11
5 224.0 g of SYLFAT® 2 (tall oil fatty acid), 630.0 g of pine oil rosin, 35.0 g of
sebacic acid, 69.0 g of succinic acid and 273.9 g of polyglycerol-3 are placed in a stirred
reactor as in Example 4. The mixture is heated to 250-270°C and the water of condensation
is removed until an acid number of less than 7 mg KOH/g is obtained. Next, 17.8 g of
succinic acid are added and the condensation is continued until an acid number of 3 mg
10 KOH/g is obtained.
Example 12
270.0 g of SYLFAT® 2 (tall oil fatty acid), 520.0 g of pine oil rosin, 47.5 g of
sebacic acid, 69.0 g of succinic acid and 273.9 g of polyglycerol-3 are placed in a stirred
15 reactor as in Example 4. The mixture is heated to 250-270°C and the water of condensation
is removed until an acid number of less than 7 mg KOH/g. Next, 17.8 g of succinic acid
are added and the condensation is continued until an acid number of 3-4 mg KOH/g is
obtained.
20 Example 13
310 g of SYLFAT® 2 (tall oil fatty acid), 475 g of pine oil rosm, 69.0 g of succinic
acid, 78.1 g of sebacic acid and 273.9 g of polyglycerol-3 are placed in a stirred reactor as
in Example 4. The mixture is heated to 250-270°C and the water of condensation is
removed until an acid number of 3 mg KOH/g is obtained.
25 The compositions of the 13 resins prepared according to Examples 1-13 are
presented in Table 2 and the corresponding physicochemical characteristics are given in
Table 3 below.
Additional Examples 14 to 17 of polyester resins for "coil" two-pack use
30
Example 14
444.0 g of Pripol® 1009, 775.5 g of hydrogenated rosin (Hydrogral®), 6.0 g of
AOX-R (phenol sulfite) and 280.5 g of polyglycerol-3 are placed in a stirred, temperatureregulated
2-liter reactor, under a nitrogen atmosphere. The mixture is heated to 250-270°C
-21-
and the water of condensation is gradually removed until an acid number of 6 mg KOH/g
is obtained. The resin is then cooled and dissolved in a mixture of Solvarex® 9 (from
TOTAL)/butyl glycol (80/20, m/m) until a final solids content of 70% is obtained. The
viscosity of the solution obtained is between 2000 and 3000 mPa.s.
5
Example 15
555.0 g of Pripol® 1009, 753.2 g of hydrogenated rosin (Hydrogral®), 6.0 g of
AOX-R (phenol sulfite) and 191.9 g of pentaerythritol are placed in a stirred, temperatureregulated
2-liter reactor, under a nitrogen atmosphere. The mixture is heated to 250-270°C.
10 The water of condensation is gradually removed until an acid number of between 6 and 10
mg KOH/g is obtained for a viscosity of between 6500 and 7500 mPa.s obtained by
dilution with a mixture of Solvarex® 9 (TOTAL)/butyl glycol (80/20, m/m) as described in
Example 14.
15 Example 16
468.8 g of Pripol® 1017, 754.6 g of pine oil rosin, 6.0 g of AOX-R (phenol sulfite),
80.0 g of succinic acid and 196.6 g of glycerol are placed in a stirred, temperatureregulated
2-liter reactor, under a nitrogen atmosphere. The mixture is heated to 250-270°C.
The water of condensation is gradually removed until an acid number of between 2 and 6
20 mg KOH/g is obtained for a viscosity of between 2000 and 3000 mPa.s obtained by
dilution with a mixture of Solvarex® 9 (TOTAL)/butyl glycol (80/20, m/m) as described in
Example 14.
Example 17
25 411.8 g of Pripol® 1009, 807.0 g of rosin FOR85, 4.5 g of AOX-R (phenol sulfite)
and 280.4 g of polyglycerol-3 are placed in a stirred, temperature-regulated 2-liter reactor,
under a nitrogen atmosphere. The mixture is heated to 250-270°C. The water of
condensation is gradually removed until an acid number of between 2 and 6 mg KOH/g is
obtained for a viscosity of between 2500 and 3000 mPa.s obtained by dilution with a
30 mixture of Solvarex® 9 (TOTAL)/butyl glycol (80/20, m/m) as described in Example 14.
The four examples, 14 to 17, correspond to four polyester resins that are variants of
the polyester described in Example 2 with a zero oil length or with an oil length of less
than 5% as defined above according to the invention, with a rosin content that is in the
-22-
region of 50% to 52%, polyesters prepared specifically for the needs of more particular
applications of coil two-pack type.
The compositions of the resins of the four examples 14 to 17 are presented in Table
2a and the physicochemical characteristics in Table 3 a.
- 2 3 -
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-28-
4) Preparation of varnish formulations based on the dispersions prepared from resins
according to Examples 1 to 13
The general procedure for preparing these varnish formulations is as follows:
150 g of aqueous binder (aqueous dispersion) as prepared according to the
5 description in point 3) above are poured into an approximately 250 ml cylindrical
container. The medium is then stirred vigorously (with a Dispermat® CV machine) at room
temperature (20-25°C). In the case of the siccativated resuis, the siccativating agent
(Durham Co 10 WM, 0.1% cobalt metal on dry binder) is added slowly and gradually with
stirring (at 700 rpm) for 5 minutes. The medium is then left to stand for 24 hours before
10 application.
5) Characterization methods used
5.1) Determination of the Tg of the resins
The glass transition temperature Tg measurement is performed using a DSC 1-700
15 type DSC machine from Mettler with a temperature sweep at 10°C/min from -80°C to
150°C and after two consecutive passages (sweeps). The Tg retained is that corresponding
to the second passage (sweep).
5.2) Molecular masses of the resins
20 The measurements are taken by steric exclusion chromatography (SEC), using THF
as eluent, under the following conditions:
two mixed columns D + one lOOA column, + one 50A column
• Elution with THF as the mobile phase, at 1 ml/min and at an elution temperature of
35°C, with detection by refractive index (RI).
25 • Calibration with 11 polystyrene standards having monodisperse molecular masses
ranging from 162 to 377 400.
5.3) Evaluation of the performance of the novel binders according to Examples 1 to 13
as aqueous dispersions
30 The hardness evaluation is performed on films obtained by applying to a glass plate
a coat of aqueous dispersion with a wet thickness of 100 |xm. These are siccativated and
non-siccativated gloss varnish formulations. The siccativating agent chosen is a cobalt•
• <
-29-
based monometallic system (Durham Co 10 WM, with 0.1 weight"/© of cobalt met,al
relative to the weight of dry resin). The dispersion used as comparative reference is an
alkyd dispersion, which is the product Synaqua® 4804 sold by Cray Valley. The
performance qualities in terms of development of hardness over time after application and
5 of evolution of the resistance to yellowing over ageing time of the novel binders are thus
compared with those of Synaqua 4804, taken as market reference in this field.
5.3.1) Preparation ofshss varnish and paint formulations based on dispersions prepared
according to Examples I to 13
10 Preparation of varnish formulations
The general procedure for preparing the varnish formulations is as follows:
150 g of aqueous binder (aqueous dispersion) prepared as above are poured into an
approximately 250 ml cylindrical container. The medium is then stirred vigorously (with a
Dispermat® CV machine) at room temperature (20-25°C). Figure 2 shows the results for
15 the hardness evolution and Table 5 shows the results for the yellowing evolution for the
non-siccativated varnishes.
For the siccativated varnishes, the siccativating agent is Durham Co 10 WM, added
at 0.1% of cobalt metal relative to the dry binder (solids content of the tested dispersion)
slowly and gradually while stirring at 700 rpm, over 5 minutes. The medium is then left to
20 stand for 24 hours before application. The results in terms of the hardness evolution for
these siccativated varnishes are presented in Figure 1.
Preparation of the gloss paint formulations
For the manufacture of a milling base, the water and the various constituents
25 detailed below are placed successively in a container with stirring at high speed in a
Disperlux model 2075 disperser, until a fineness < 10 jiim is obtained.
For the manufacture of paint, the binder (tested dispersion), the milling base
prepared previously, the water and the various constituents are placed successively in a
container with stirring. The siccativating agent (Borcher Oxi-Coat) is added slowly and
30 gradually with stirring (at 700 rpm) over 5 minutes to about 1.5% for the dispersions of the
invention and 0.25% for the reference Synaqua 4804® (percentage expressed relative to the
-30-
dry binder) in order to obtain a series of dry paints that can be recoated 6 hours after
application. The composition of the paint formulation is presented below.
Composition of the paint formulations of resin dispersions of Examples 1 to 13
5
^ ,., , T^ ,. Parts by weight
Constituent Function .„.. "
Lz»i
Water - 4.50
ACTICIDE MBS Biocide 0.20
DISPERBYK 190 Dispersant 0.58
BYK022 Antifoam 0.10
TIONA 595 Pigment 23.00
Total milling base 28.38
Tested dispersion - 60.50
BORCHI'^ OXY-COAT* Siccativating agent 0.45*
Water - 8.81
AQUAFLOW^ NMS 450 Thickener 0.75
AQUAFLOW^ NHS 300 Thickener 1.15
Total paint | | 100
* amount for reference resin Synaqua 4804 adjusted corresponding to 0.25% relative to the dry binder
(solids content of the resin dispersion). ,
Characteristics of formulations (calculated by means of the formulation software "PV-
10 FORMULA Version 2-3" from Pierre Vergne - Inter Deposti Digital Number:
IDDM.FR.001.280022.001.S.P.2001.0003.030265):
Volume-based pigment concentration: VPC = 19%
Solids content by weight = 51.1%
SoHds content by volume = 38.1%
15 Density d= 1.26
Comparative tests of yellowing evolution were performed on these formulations,
and the results are presented in Table 6.
- 3 1 -
5.3.2) Hardness test: accordinz to the method ISO 1522
This is a Persoz hardness determined at 23°C and at 50% relative humidity. The
varnishes are applied at a wet thickness of 100 \im and are then dried on a perfectly
horizontal surface at 23°C and at a relative humidity of 50% for 24 hours before the first
5 measurement.
5.3.3) Measurement of the yellowing: accordins to the Yellowing index (Yi) method ASTM
E313-96
The yellowing measurements are taken on a Leneta 2A card with a wet thickness of
10 150 i^m. The surface is then dried totally horizontally at 23°C and at 50% relative humidity
for 24 hours before the measurement using a Minolta CM2600D spectrocolorimeter
(measurement on the white part of the card). The yellowing is then accelerated by placing
the Leneta cards in an oven at 50°C in the absence of light, for 15 days.
15 5.3.4) Blocking resistance
The blocking resistances are determined on a Leneta 2A card with a wet thickness
of 150 ]im. For this test, two films of gloss paint are applied (preparation detailed in point
5.3.1) with replacement of the siccativating agent BORCHI® OXY-COAT with Durham Co 10
WM (0.1% cobalt metal on dry binder)) on separate Leneta cards, which are then
20 positioned after 24 hours of drying at room temperature face to face so that the paints are
in contact. A weight of 50 g.cm""^ is then placed on the two cards that are face-to-face,
exerting a pressure of 50 g.cm"'^. After 24 hours of contact, the two Leneta cards are
separated and examined. The result obtained is expressed qualitatively as a fiinction of the
total surface area of white paint peeled off, with a note ranging from 0 (0 = no point of
25 peeling) to 8 (8 being the worst note with the plate highly degraded).
6) Results for development of hardness, resistance to yellowing and blocking
resistance for coatings based on aqueous dispersions obtained from the resins
according to Examples 1 to 13
30
The results as regards the development of hardness are presented in figures 1 and 2,
respectively, for siccativated and non-siccativated varnishes.
- 3 2 -
The results as regards the yellowing on varnishes whose formulation is specified in
point 5.3.1) without siccativating agent are presented in Table 5 for the binders not
requiring any siccativating agent in order to dry (touch-dry < 24 hours) and having an oil
length up to 15% (resins from Examples 1 to 9).
5 The yellowing results for all of the binders of the invention for a siccativated gloss
paint formulation, as described in point 5.3.1), are presented in Table 6. The content of
siccativating agent is adjusted and optimized to obtain a dry paint that can be recoated after
6 hours.
10 Table 5: Yellowing evolution of non-siccativated varnishes
Synaqua®
Resin Ex 1 Ex 3 Ex 4 Ex 5 Ex 6 Ex 7 Ex 8 Ex 9 4804
(reference)
Yellowing
+58% +37% +58% +92% +90% +54% +115% +120% +137%
evolution
Table 6: Yellowing evolution of gloss paints
\ \ \ I F v I I \ \ \ I Synaqua®
Resin Ex 1 Ex 2 Ex 3 ^ Ex 8 Ex 9 Ex 10 Ex 11 Ex 12 4804
(reference)
Yellowing
evolution +58 +34 +34 +80 +67 +60 +90 +75 +100 +150
(%)
15
The capacity to cure faster for the novel aqueous binders of the invention is even
more perceptible and notable in the absence of siccativation (see figure 2). Figure 2
illustrates the development of hardness for the aqueous binders based on resins having the
shortest oil length ranging from 0 to 15%, which means a zero oil length (0%) or an oil
20 length ranging up to 15%, which is quite surprising given these very low or even zero
contents. In contrast, it is noted that the resins with an oil length of about 15%) to 30%
require the use of siccativating agent in order to develop their high hardness potential. On
the other hand, good or even excellent levels of hardness may be recorded without
1
- 3 3 -
supplying siccativating agent, using resins with a low or even zero oil length (0-15%) (see
figure 2).
In general, these novel resins show rapid development of hardness with hardness
levels (at 15 days) largely superior to those of the reference dispersion Synaqua® 4804. For
5 some of them (among the smallest oil lengths), the final hardnesses reached without using
siccativating agent are even identical to or greater than that of the siccativated reference
resin (4804®). This capacity to cure greatly, without necessary supply of siccativating
agent, is a major advantage in the current environmental context.
Advantageously, faced with the toxicity problems experienced with cobalt salts,
10 these dispersions can dry with less harmful siccativating agents (which are for the majority
less active when compared with the conventional cobalt-based systems) such as iron salts
(Borcher Oxy-Coat), vanadium or manganese salts. Much more advantageously, certain
resins (0-15%) can dry and cure with high performance levels without the need for any
' siccativating agent.
15 Still advantageously, these resins with a greatly reduced oil length, in the absence
or presence of siccativating agent, show less yellowing evolution over time (see the details
in Table 5 and 6 above) when compared with the reference resin (Synaqua® 4804).
Figure 1 shows the evolution over time, after application, of the hardness of the
coatings obtained for coating compositions (varnishes described above) in the presence of
20 siccativating agent. The dispersions according to the invention have at least the same if not
better performance in terms of rapid growth of the hardness over time (in particular for the
range of dispersions based on resins with an oil length from 0 to 15%) than that of the
reference dispersion (based on Synaqua^ 4804 resin) despite a higher oil length for the
latter.
25 Figure 2 shows even better the performance of the dispersions according to the
invention in the total absence of siccativating agent on varnishes. The reference dispersion
is also represented in the presence of siccativating agent (0.1%) to show that the
dispersions corresponding to an oil length ranging from 0 to 15%, in the absence of any
siccativating agent, show better performance (on varnishes) than the reference dispersion
30 even when comparing the latter in the presence of 0.1% siccativating agent (comparative
conditions more unfavorable for the dispersions of the invention).
f
- 34 -
Advantageously, the resins with an oil length ranging from 15% to 25%,
siccativated with cobalt as described above, show excellent blocking resistance in
particular relative to the reference resin (Synaqua® 4804). Figure 3 explicitly and
qualitatively sliows this marked difference in blocking resistance between a dispersion
5 prepared according to Example 11 (in the left part of figure 3) and the reference resin
(Synaqua 4804 in the right part). Surprisingly, the resin of the invention under these
conditions does not lead to any point of attachment or peeling of the coating during the
blocking resistance test (note = 0), in contrast with the reference resin (note = 8). Since the
application support for the white paint is black, this means that the black parts of the image
10 in figure 3 correspond to the parts peeled off during the test (right part with note = 8). In
the case of the resin dispersion according to Example 11, the white image demonstrates the
absence of any peeling (note = 0).
7) Evaluation of the resins of zero oil length ("oil free"") or with an oil length ranging
15 up to 5%. in a "coil" two-pack system
The resins concerned are described in Example 2 and in Examples 14 to 17, which
are variants of the resin of Example 2 as described above.
7.1) Preparation of non-water-based formulations for "coil" two-pack coatings
("varnishes)
20 The solvent-based solutions (translucent) of the resins described according to
Examples 14 to 17 are mixed with melamine CYMEL® 303 LF in an 85/15 weight ratio (of
dry resin to melamine).
Formulation example:
Resin (NVC 69.7%) \ 73J
Solvarex 10 LN 8~
BUTYLDIGLYCOL 8
CYMEL 303 LF 9
PTSA(12.5%butanol) L3
Total 100
25 The varnishes are then applied in order to have a film thickness of 20 \im ± 2 \im
on galvanized steel GARDOBOND Ref 1303 62 OE, 0.8 mm thick, and are then baked in
-35-
an oven heated to 315°C in order to reach a maximum temperature of the support metal of
232°C before cooling.
7.2) Evaluation of the performance of the binders of zero oil length ("oil-free") or with
5 an oil length ranging up to 5%, in a coil tvyo-pack system
7.2.1) Methods and tests used
a) Chemical resistance to MEK (Methyl Ethyl Ketone)
The solvent resistance is evaluated by wearing the surface of the samples with a pad
of cotton wool soaked with MEK by performing to-and-firo motions on the coatings as
10 described in point 7.1). The test is performed at a frequency of 60 cycles/minute (1 to-andfro
motion per second) with a load of 1 kg on a linear abrasimeter. The time measured
corresponds to the time for which the film of paint withstood the abrasion in the presence
of the solvent.
15 b) Adhesion test
The adhesion test and the grading are performed according to standard ISO
2409:2007 using a 3M reference 2525 adhesive tape (adhesive power: 700 cN/cm).
Adhesion grading: scale from 0: good, to 5: poor. The test is repeated a second time
(results presented in Table 7).
20
c) Adhesion test with collar and ageing at 90°C
1) Stamping 7 mm deep at the precise place of the adhesion test is performed, using a
Cupping Tester ELCOMETER 1620 type stamping machine equipped with a
hemispherical-shaped punch 20 mm in diameter rising at a speed of 0.2 mm/s, on a
25 galvanized steel plate (dimensions 100 mm x 60 mm) covered with the coating as
described in point 7.1).
2) The plate is then placed in an oven at 90°C for 30 minutes. After cooling for 30
minutes in an air-conditioned room (23 °C ± 2 °C and 50% ± 5 % RH), an adhesion
test is performed according to standard ISO 2409.
30
The whole test is repeated a second time, and the results are given in Table 7.
«
J
-36-
d) Hardness test (Persoz)
Measurement of the damping of the pendulum (1 oscillation/s) according to NF EN
ISO 1522 (of. description of the test in point 5.3.2).
5 7.2.2) Results obtained
These resuhs are presented in Table 7 below:
Table 7: Results for application on galvanized steel
\ Synolac® \ \ \ \ \ P
Example 2 14 15 16 17
9605 S 65
Chemical
resistance to 80s 140 s 140 s 100 s 120 s 170 s
MEK*
Adhesion test
0/0 0/0 0/0 0/0 0/0 0/0
(ISO 2409)
Adhesion test
with collar
2/2 0-1/0-1 0-1/0-1 0-1/0-1 0-1/0-1 0-1/0-1
and ageing at
90°C
Persoz
hardness (ISO 296 s 340 s 350 s 312 s 320 s 332 s
1522)
* Methyl ethyl ketone
10
The resin described in Example 2 and the resins according to Examples 14 to 17 all lead,
without exception, to very high performance in terms of hardness, chemical resistance and
adhesion to metal (galvanized steel in the case of this application), better than those of the
reference resin for coil application (Synolac® 9605 S 65). Firstly, the adhesion is found to
15 be very greatly reinforced on metal by virtue of the incorporation of materials such as rosin
and fatty acids (essentially dimers) all of natural origin. The high performance recorded
regarding the hardness in a coil two-pack system confirms the substantial gain in hardness
observed on the coatings (varnishes) obtained from the aqueous dispersions dried in the
open air (see figures 1 and 2).

CLAIMS
1. A polyester resin, in particular an alkyd resin, characterized in that it:
is based on at least one fatty acid
5 - has a zero oil length (0%) or an oil length between 0 and 35%, preferably greater
than 0 and up to 25%, more preferentially up to 15%
has a weight ratio of oxidizable fatty acids (monoacids) relative to the overall fatty
acids of 0 or more than 0 and ranging up to 1
is based on an acid component comprising, in addition to said fatty acid, from 30%
10 to 85%, preferably from 35% to 75%, more preferentially from 40% to 75% and
even more preferentially from 45% to 75% by weight, relative to the total weight of
said resin, of rosin and/or rosin derivatives bearing at least one carboxylic acid
function.
2. The resin as claimed in claim 1, characterized in that it comprises less than 5%,
15 preferably less than 3% by weight and more preferentially no (%) aromatic
compound besides the optional rosin derivatives.
3. The resin as claimed in claim 1 or 2, characterized in that it is based on an acid
component comprising, in addition to said fatty acid, said rosin and/or in addition
to said rosin derivatives, at least one acid compound containing at least one
20 carboxylic acid flinction and having an overall functionality of 2 to 3, chosen from:
saturated polyacids or ethylenically unsaturated poly acids or hydroxy acids.
4. The resin as claimed in claim 3, characterized in that said acid component
comprises at least two from among said acid compounds, with at least one chosen
from saturated polyacids and at least another chosen from unsaturated polyacids, in
25 addition to said fatty acid and said rosin and/or said rosin derivatives.
5. The resin as claimed in claim 3 or 4, characterized in that said saturated polyacid is
chosen from the acid and/or anhydride corresponding to: succinic acid, adipic acid,
sebacic acid, dodecanedioic acid, citric acid, C36 fatty acid dimer, C54 fatty acid
trimer.
30 6. The resin as claimed in claim 3 or 4, characterized in that said unsaturated polyacid
is chosen from the existing acid and/or anhydride corresponding to: itaconic acid,
maleic acid or fumaric acid or tetrahydrophthalic acid (THP).
t
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7. The resin as claimed in one of claims 3 to 6, characterized in that said polyacid
comprises at least one C36 fatty acid dimer and/or C54 fatty acid trimer.
8. The resin as claimed in one of claims 3 to 7, characterized in that said acid
component also comprises at least one of said acid compounds chosen from
5 hydroxy acids, preferably from glycolic acid or lactic acid.
9. The resin as claimed in one of claims 1 to 8, characterized in that the oxidizable
unsaturation content of said resin is zero (0) or is greater than 0 and up to 0.25 and
preferably up to 0.15 mmol of oxidizable double bonds per g of dry resin.
10. The resin as claimed in one of claims 1 to 9, characterized in that it is based on an
10 alcohol component comprising at least one polyol of functionality ranging from 2
to 10 and preferably from 3 to 6.
11. The resin as claimed in claim 10, characterized in that said polyol is selected from:
ethylene glycol, polyethylene glycol (preferably with an Mw of from 300 to 6000),
propylene glycol, 1,3-propanediol, dipropylene glycol, triethylene glycol, glycerol,
15 diglycerol, trimethylolpropane (or -ethane), pentaerythritol, dipentaerythritol,
sorbitol, mannitol, methyl glucoside, polyglycerol, in particular glycerol oligomers
such as polyglycerol-3 (glycerol trimer) and decaglycerol, and preferably glycerol
oligomers, and more particularly polyglycerol-3 (glycerol trimer).
12. The resin as claimed in one of claims 1 to 11, characterized in that it has an acid
20 _ number of less than 8 and a number-average molecular mass Mn, measured by
GPC as polystyrene equivalents in THF, ranging from 1000 to 10 000.
13. The resin as claimed in one of claims 1 to 12, characterized in that it has a Tg,
measured by DSC, ranging from -40 to 50°C and preferably from -20 to 35°C.
14. The resin as claimed in one of claims 1 to 13, characterized in that said oil length is
25 between 0 and 35%, and preferably is greater than 0 and ranges up to 25% and
more preferentially up to 15%, with the presence of at least one oxidizable fatty
acid (monoacid).
15. The resin as claimed in claim 14, characterized in that the oxidizable unsaturation
content of said resin is greater than 0 and up to 0.25 and preferably up to 0.15
30 mmol of oxidizable double bonds per g of dry resin.
t • I
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16. The resin as claimed in claim 14 or 15, characterized in that said fatty acid is
selected from fatty monoacids of plant or animal origin, which are preferably of Ci6
to C24, with a mean iodine number ranging from 100 to 200.
17. The resin as claimed in one of claims 14 to 16, characterized in that said fatty acid
5 is selected from fatty acids of soybean oil, sunflower oil, tall oil (TOFA), castor oil,
dehydrated castor oil, Imseed oil or rapeseed oil, said fatty acids being used as such
or in the form of corresponding oils (triglyceride esters) of fatty acids or of
corresponding stand oils of fatty acid oils.
18. The resin as claimed in one of claims 14 to 17, characterized in that it is based on a
10 polyacid comprising at least one C36 fatty acid dimer and/or C54 fatty acid trimer
and based on a polyol comprising at least one glycerol and/or pentaerythritol and/or
dipentaerythritol oligomer, preferably glycerol trimer, more particularly
polyglycerol-3.
19. The resin as claimed in one of claims 1 to 18, characterized in that said polyester is
15 an aljcyd resin with an oil content of greater than 0%, preferably up to 25% and
more preferentially up to 15%.
20. The resin as claimed in one of clauns 1 to 13, characterized in that said resin has a
zero oil content (0%) and in that said fatty acid is selected from non-oxidizable
fatty acids with a corresponding content of oxidizable unsaturations that is 0 mmol
20 per g of dry resin or in that said resin has an oil content ranging up to 5% and that,
in addition to said fatty acid selected from non-oxidizable fatty acids, it comprises
in minor weight proportions an oxidizable fatty acid leading to said oil content
ranging up to 5%.
21. The resin as claimed in claim 20, characterized in that said non-oxidizable fatty
25 acid is selected from saturated fatty acids, including fatty acids that are initially
oxidizable which have been hydrogenated or from fatty acid oligomers, preferably
C36 dimers (including hydrogenated dimers) and/or C54 trimers (including
hydrogenated trimers).
22. The resin as claimed in claim 20 or 21, characterized in that said resin is based on
30 an alcohol component comprising as polyol a glycerol oligomer,' preferably
polyglycerol-3, and as non-oxidizable fatty acid a C36 fatty acid dimer and/or a C54
fatty acid trimer (which are hydrogenated or non-hydrogenated).
<
-41-
23. An organic binder composition, characterized in that it comprises at least one resin
as defined according to one of claims 1 to 22.
24. The composition as claimed in claim 23, characterized in that, in addition to the
first resin as defined according to one of claims 1 to 22, it comprises at least one
5 second resin different fi"om the first, with this second resin being selected from
polyester resins based on fatty acids, preferably from modified alkyd resins.
25. The binder composition as claimed in claim 23 or 24, characterized in that said first
resin is as defined according to one of claims 20 to 11.
26. An aqueous dispersion of resin, characterized in that it comprises at least one resin
10 as defined according to one of claims 1 to 22 or at least one binder composition as
defined according to one of claims 23 to 25.
27. The aqueous dispersion as claimed in claim 26, characterized in that it comprises,
in addition to said resin or said binder composition, at least one surfactant selected
from: at least one anionic surfactant and at least one nonionic surfactant or at least
15 one surfactant of mixed structure and with an overall weight ratio relative to said
resin ranging from 2% to 15% and preferably fi-om 5% to 10%.
28. The dispersion as claimed in claim 26 or 27, characterized in that it has a solids
content ranging from 30% to 70%) and preferably from 40%) to 60%) and a mean
particle size ranging from 100 to 500 nm.
20 29. The dispersion as claimed in one of claims 26 to 28, characterized in that it is free
of any organic solvent with a corresponding VOC content of less than 1000 ppm,
preferably less than 500 ppm and more preferentially less than 100 ppm.
30. An aqueous dispersion of resin, characterized in that it comprises as a mixture a
first aqueous dispersion of resin as defined according to any one of claims 26 to 29
25 and at least one second resin dispersion different from the first, this second resin
dispersion being selected from optionally modified alkyd dispersions, acrylic
(including styrene-acrylic) dispersions (or emulsions) or dispersions of other
polymers and in particular saturated or unsaturated polyester or polyurethane
dispersions.
30 31. The dispersion as claimed in claim 30, characterized in that the weight content of
said first dispersion ranges from 50%o to 99.5%).
I
- 42 -
32. The dispersion as claimed in one of claims 26 to 31, characterized in that it is free
of any protective colloid.
33. A process for preparing an aqueous dispersion as defined according to one of
claims 26 to 29, characterized in that it comprises a step of emulsification, at a
5 temperature of fi:om 30 to 90°C and preferably from 50 to 85°C, of at least one
resin as defined according to one of claims 1 to 22 and/or of at least one organic
binder composition as defined according to one of clakns 23 to 25, by phase
inversion in a reactor stirred via a dual-flow stirring system.
34. A coating composition, characterized in that it comprises as binder at least one
10 resin as defined according to one of claims 1 to 22 or at least one binder
composition as defined according to one of claims 23 to 25 or at least one aqueous
dispersion as defined according to one of claims 26 to 32.
35. The composition as claimed in claim 34, characterized in that said composition is a
water-based coating composition.
15 36. The coating composition as claimed in claims 34 and 35, characterized in that said
coating is selected fi-om decorative or industrial coatings, in particular for industrial
coatings including anticorrosion coatings, preferably from water-based coatings:
adhesives, paints, surface coatings, primers and varnishes.
37. The coating composition as claimed in one of claims 34 to 36, characterized in that
20 it is based on an aqueous dispersion as defined according to one of claims 26 to 32,
in that it comprises a siccativating agent and in that said resin used as binder has an
oil length (content) ranging up to 25% and preferably fi-om 15% to 25%.
38. The coating composition as claimed in claim 34, characterized in that it comprises
as binder at least one resin as defined according to one of claims 20 to 22 or at least
25 one binder composition as defined according to claim 25.
39. The coating composition as claimed in claim 38, characterized in that it is a
protective coating for coil applications.
40. The use of at least one resin as defined according to one of claims 1 to 22 or of a
binder composition as defined according to one of claims 23 to 25 or of at least one
30 aqueous dispersion as defined according to one of claims 26 to 32, characterized in
that it concerns use as a binder in coatings.
«
- 4 3 -
41. The use as claimed in claim 40, characterized in that it concerns decorative or
industrial water-based coatings selected ftom adhesives, paints, surface coatings,
primers or varnishes.
42. The use as claimed in claim 41, characterized in that it concerns coatings for
5 substrates selected from: v^ood, metals, plaster, concrete, composites or plastics.
43. The use as claimed in claim 40, characterized in that the resin used as binder is as
defmed according to one of claims 20 to 22 or in that the binder composition used
is as defined according to claim 25 and in that it concerns use as a binder in twopack
coatings, more particularly for coil applications and even more particularly in
10 marine and anticorrosion applications.
44. A substrate coating, characterized in that it is obtained from at least one resin as
defined according to one of claims 1 to 22 or from at least one binder composition
as defined according to one of claims 23 to 25 or from at least one dispersion as
defmed according to one of claims 26 to 32.