The present invention relates to a composition, more
specifically a composition based on amines, enabling
5 the neutralization of aqueous fluids, such as aqueous
dispersions of mineral fillers, metal working fluids,
and others, while limiting or preventing bacterial
growth and proliferation in said aqueous fluids.
10 With the ever expanding development ,of paints, inks,
varnishes and other coatings that are solvent-free or
that have a reduced content of solvent, it is necessary
to be able to disperse mineral fillers in water. The
technique of dispersing mineral fillers in water is a
15 technique that is today well known, but the dispersions
that result therefrom can pose some problems.
Indeed, in aqueous paints, such as acrylic-based latex
paints, a pH adjustment is generally necessary in order
20 to stabilize the latex. This adjustment is referred to
as neutralization. Furthermore, when a pigment
concentrate is diluted in a white paint or white base,
whether it be aqueous or solvent-based, it is also
necessary to neutralize these pigment concentrates.
25
In the paper industry, it is also necessary to
neutralize the aqueous dispersions of mineral fillers
intended for coating paper, due to the acidity of the
dispersion agents used, such as for example the
30 dispersion agents Coatex® P90 from Coatex or Dysperbyk®
191 or BYK® 192 from BYK-Chemie GmbH, or Orotan™ 850ER
from Rohm & Haas.
As neutralizing agent, use is commonly made of ammonia,
35 sodium hydroxide, dimethylamine, monoethanolamine,
diethanolamine and N-methylethanolamine. Other
neutralizing agents that have arrived more recently on
the market are alkylalkanolamines, among which mention
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may be made of 2-amino-2-methyl-l-propanol (CAS
No. 124-68-5), sold under the trademark AMP® at 90% or
95% in water under the names AMP® 90 and AMP® 95
respectively, by Angus, or else N-n-butyl-N-(2-
5 hydroxylethyl)amine and N-(1-methylpropyl)-N-(2-
hydroxyethyl)amine, sold by Arkema under the name
Alpamine™ N41.
These neutralizing agents, which are generally mineral
10 or organic bases, commonly used today, have the
advantage of being perfectly soluble in water and
enable an effective neutralization of the agueous
dispersions of mineral fillers.
15 Typically, the pH of a latex is ideally adjusted to a
value between 8 and 10, preferably between 8.5 and 9.5
when the neutralizing amine (adjusting amine) is added
in a proportion of from 0.1% to 0.5% by weight,
preferably from 0.1% to 0.3%, more preferably from 0.1%
20 to 0.2%. In pigment concentrates, the amount of
codispersant amine is, preferably, kept below 3.5% by
weight.
However, these agueous dispersions may become unstable,
25 especially due to bacterial growth and the
proliferation of bacteria which may occur within them.
The expression "bacterial growth and bacterial
proliferation" is understood, within the meaning of the
present invention, to mean the growth and proliferation
30 of bacteria, the growth and proliferation of
mycobacteria, fungal growth and proliferation, and in
general any growth and proliferation of living
organisms, capable of destabilizing the agueous fluids,
of coloring them, of giving them an unpleasant odor, of
35 thickening them, of rendering them non-homogeneous, and
more generally of rendering them unsuitable for the
uses thereof for which they were conceived.
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Therefore, the addition to these aqueous fluids of one
or more biostatic agents (that prevent the
proliferation of bacteria if they have appeared) and/or
biocidal agents (agents that "kill" bacteria, thus
5 preventing the appearance of bacteria) is recommended.
The biostatic and/or biocidal agents commonly used
today are typically biocides based on formaldehyde,
glutaraldehyde and/or isothiazolone, for example those
sold by Thor under the name Acticide®.
10
These biostatic and/or biocidal agents are perfectly
soluble in aqueous media and perfectly compatible with
the neutralizing agents set out above.
15 However, some of these biostatic and/or biocidal agents
may lead to pH stability problems, and some are now
considered to be harmful or dangerous for the
environment; the environmental regulations in force or
to come require their partial or complete replacement
2 0 by compounds that are not harmful and not dangerous for
the environment.
In patent US 4,925,582, it is indicated that certain
amines, which can be used in industrial hydraulic
25 fluids and/or as neutralizing agents, exhibit
antibacterial properties, thus making it possible to
reduce the effective amount of environmentally harmful
biocides.
30 Although these amines can be considered to be
sufficiently compatible with aqueous fluids, soluble in
aqueous media and sufficiently basic to enable the
neutralization of the aqueous fluids when necessary,
these amines do not however exhibit a satisfactory, or
35 even sufficient, antimicrobial action.
There therefore remains a need for additives for
aqueous fluids that exhibit both a neutralizing action
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and a biostatic action, that is to say agents that
prevent or limit (myco)bacterial and/or fungal
proliferation.
5 Thus, a first objective of the invention is to provide
novel biostatic neutralizing agents in aqueous fluids
which are effective, both as regards the adjustment of
the pH of said aqueous fluids and as regards
(myco)bacterial and/or fungal anti-proliferation within
10 said aqueous fluids, and which are in addition
perfectly compatible with said aqueous fluids.
Yet other objectives will appear in the description of
the invention which follows.
15
The Applicant has now discovered that these objectives
may be achieved completely or partly owing to the
compositions according to the present invention.
20 Thus, a first subject of the present invention is a
biostatic neutralizing composition for aqueous fluids
comprising at least one organic or mineral base (B) and
at least one amine of formula (2):
f'" ""OH
R ' OH /^^
25 \^f
wherein R^ represents a linear or branched hydrocarbonbased
radical, preferably a linear or branched alkyl
radical, having 7, 8, 9, 10, 11 or 12 carbon atoms.
30
The base (B) may be of any type known per se, and, as
non-limiting examples, the mineral bases may
advantageously be chosen from alkali metal hydroxides
or alkaline-earth metal hydroxides, in particular from
35 sodium, potassium or calcium hydroxide, and nitrogenous
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bases, preferably bases comprising at least one amine
group, more preferably 1 amine group.
As a variant, the base (B) may be an organic base, such
5 as those commonly used by a person skilled in the art,
in particular nitrogenous bases, for example ammonium
hydroxide, and more particularly the bases comprising
at least one amine group, more preferably 1 amine
group.
10
According to one preferred aspect of the present
invention, the base (B) is an organic base, quite
preferably the base (B) is an amine of low molecular
weight, that is to say, within the meaning of the
15 present invention, an amine having a total number of
carbon atoms of less than or equal to 10, preferably a
total number of carbon atoms of less than or equal to
9. For the requirements of the invention, cyclic amines
are not preferred.
20
The amines of low molecular weight are preferably
monoamines and may be primary, secondary or tertiary
amines. The nitrogen atom may be substituted by 1
hydroxyalkyl radical or 2 hydroxyalkyl radicals, or
25 even 3 hydroxyalkyl radicals, preferably by 1 or 2, or
even 3 hydroxyethyl radicals, more preferably 1 or 2
hydroxyethyl radicals, more preferably still 2
hydroxyethyl radicals.
30 More preferably still, the base (B) is an amine of
formula (1):
H
R R ^^j
35 wherein:
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• either. R^ represents a linear or branched
hydrocarbon-based radical, preferably a linear or
branched alkyl radical, having 1, 2, 3, 4, 5 or 6
5 carbon atoms, and R^ and R"^ each represent the
radical - (CH2-CH2)-OH,
• or R"*" represents a hydrogen atom and R^ represents
a hydrogen atom and R'^ represents the radical
-(CH2-CH2)-OH.
10
In one particularly preferred embodiment, a subject of
the present invention is a biostatic neutralizing
composition for aqueous fluids comprising at least one
amine having a total number of carbon atoms of less
15 than 10, preferably of less than 9, preferably at least
one amine of formula (1) and at least one amine of
formula (2) :
N N
R^- -R* ... R2-- ---^ '-OH „,
20
in which R^, R^, R""" and R^ are as defined previously.
The expression ^^neutralizing composition" is understood
to mean a composition capable of neutralizing an acidic
25 aqueous fluid, or else capable of adjusting the pH of
an acidic aqueous fluid.
The expression "biostatic composition" is understood to
mean a composition capable of preventing or at the very
30 least limiting bacterial, mycobacterial and/or fungal
proliferation of an aqueous fluid.
The expression "aqueous fluid" is understood to mean
any type of industrial aqueous fluid, and in
35 particular, as non-limiting examples, white bases of
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aqueous or aqueous-organic paints, aqueous pigment
concentrates, aqueous dispersions of mineral fillers,
metal working fluids, abrasive fluids for polishing
glass (mirrors) and others.
5
The amines of formula (1) are known in themselves and
are either commercially available or easily prepared
from procedures that are known or readily accessible to
a person skilled in the art in patent literature,
10 scientific articles, scientific works. Chemical
Abstracts or else on the Internet.
Among the amines of formula (1), within the context of
the present invention, butylamine, hexylamine,
15 (2-ethyl)hexylamine, monoethanolamine (MEA), N-(nbutyl)-
N-hydroxyethylamine, N-(sec-butyl)-N-hydroxyethylamine,
methyldiethanolamine (MDEoA),
ethyldiethanolamine (EDEoA), propyldiethanolamine
(PrDEoA), butyldiethanolamine (BDEoA),
2 0 pentyldiethanolamine (PDEoA) and hexyldiethanolamine
(HDEoA) are very particularly preferred, and very
particularly preferably, the amine of formula (1) is
chosen from monoethanolamine (MEoA),
(2-ethyl)hexylamine and methyldiethanolamine (MDEoA).
25
The amines of formula (2) are known in themselves and
are either commercially available or prepared easily
from procedures that are known or readily accessible to
a person skilled in the art in patent literature,
30 scientific articles, scientific works. Chemical
Abstracts or else on the Internet.
The amines of formula (2) may, for example,
advantageously be obtained by reductive amination of a
35 ketone or of an aldehyde by a primary amine or a
primary hydroxyalkylamine, as described in
international application PCT/FR2010/051299.
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Among the amines of formula (2) , within the context of
the present invention, n-heptyldiethanolamine (C7DE0A),
n-octyldiethanolamine (CsDEoA), 2-(ethyl)hexyl-
5 diethanolamine (C2-6DE0A), n-decyldiethanolamine
(CioDEoA) , n-undecyldiethanolamine (CuDEoA) and ndodecyldiethanolamine
(C12DE0A) are very particularly
preferred. Very particularly preferably, the amine of
formula (2) is n-heptyldiethanolamine (C7DE0A).
10
According to one preferred embodiment of the present
invention, the biostatic neutralizing composition
comprises:
a) at least one mineral or organic base, preferably
15 an organic base, and more preferably an aminecontaining
base, chosen from sodium hydroxide,
potassium hydroxide, calcium hydroxide, aqueous
ammonia, monoethanolamine (MEoA), (2-ethyl)hexylamine
and methyldiethanolamine (MDEoA); and
20 b) at least one second amine of formula (2),
preferably n-heptyldiethanolamine (C7DE0A).
Compositions comprising monoethanolamine (MEoA) and
n-heptyldiethanolamine (C7DE0A) or compositions
25 comprising methyldiethanolamine (MDEoA) and
n-heptyldiethanolamine (C7DE0A) are very particularly
preferred.
In the compositions according to the present invention,
30 the base (B)/amine (2) molar ratio, and in particular
the amine (1)/amine (2) molar ratio, is generally
between 1:99 and 99:1, preferably between 1:9 and 9:1.
The molar ratio defined here generally depends on the
nature of the aqueous fluid, on its degree of acidity,
35 on the desired biostatic effect, on the temperature,
and others. This molar ratio will be able to be
optimized easily by a person skilled ^Ln the art.
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According to one very particularly preferred
embodiment, this molar ratio is advantageously between
1.5 and 3.
5 In practice, and especially when the base (B) is an
amine of low molecular, the compositions according to
the invention comprise from 40% to 99% by weight of at
least one amine of low molecular weight and from 1% to
60% by weight of at least one amine (2) , relative to
10 the total weight of the composition.
According to another preferred aspect, these
percentages range respectively from 50% to 80% by
weight for the amine of low molecular weight and from
15 20% to 50% by weight for the amine (2) and more
preferably from 60% to 80% by weight, and from 20% to
40% by weight respectively.
The amines of formula (2) possess quite advantageous
20 biostatic properties, but are only weakly soluble or
are insoluble in water and have neutralizing properties
that are usually insufficient. The bases (B) , and in
particular the amines of formula (1) , on the other hand
are soluble in water and have a perfectly satisfactory
25 neutralizing capacity.
The Applicant has now discovered, unexpectedly, that
the combination of at least one base (B), preferably at
least one amine of formula (1), with at least one amine
30 of formula (2) gives the composition highly
advantageous properties, and in particular very good
neutralizing properties, very good biostatic
properties, and also an excellent solubility in water.
35 Without wishing to be tied to the theory, the base (B),
and in particular the amine of formula (1), acts as a
co-solvent in water for the amine of formula (2).
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Thus, the biostatic neutralizing compositions according
to the invention have the very great advantage of
making available to the final user a composition that
is homogeneous, stable over time, and miscible in
5 water, and that therefore requires only a single oneoff
addition of a solution to an aqueous fluid in order
to be able both to adjust its pH and limit, or even
prevent, bacterial proliferation within it.
10 Another advantage linked to the biostatic neutralizing
compositions according to the invention is their
dispersing power, or more precisely their co-dispersing
power, when said compositions are used in aqueous
dispersions of mineral fillers.
15
The compositions according to the present invention may
be in concentrated form or diluted in water or in a
water-soluble organic solvent or else in an aqueousorganic
solvent, in any proportions, depending on the
20 envisaged use.
The compositions according to the present invention may
in addition comprise one or more additives commonly
used in the envisaged fields of application. Among the
25 additives that may be added to the compositions
according to the present invention, mention may be
made, as non-limiting examples, of co-solvents,
surfactants, colorants, stabilizers, mineral or organic
bases, biocides, UV stabilizers, and others.
30
According to a second aspect, the present invention
relates to the use,^ as a biostatic neutralizing
additive, of a composition comprising at least one
base, preferably at least one amine of low molecular
35 weight, more preferably at least one amine of formula
(1), and at least one amine of formula (2) as described
previously for an industrial aqueous fluid.
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The biostatic and neutralizing effect of the industrial
aqueous fluid is obtained by simple introduction and
optional mixing into said industrial aqueous fluid of
an effective amount of a composition according to the
5 present invention.
The expression "effective amount" is understood, in the
preceding paragraph, to mean an amount generally of
between 0.0001% and 10% by weight of biostatic
10 neutralizing composition relative to the total weight
of the industrial aqueous fluid, preferably between
0.001% and 5% by weight. However, this amount depends
on the envisaged application and on the desired effect.
Thus, in general, this amount may be between 0.001% and
15 1%, preferably between 0.003% and 0.5% by weight, for
example around 400 ppm by weight in the case of aqueous
dispersions of mineral fillers; in the case of aqueous
metal working solutions, this amount may be between 3%
and 5% by weight.
20
Owing to their neutralizing, biostatic, water-soluble
and co-dispersing capacities, the compositions
according to the present invention find particularly
suitable uses in industrial fluids of any type, such as
2 5 for example those described above.
According to yet another aspect, the present invention
relates to an industrial fluid comprising at least one
biostatic neutralizing composition according to the
30 present invention, the amount of said composition in
said industrial fluid being as indicated previously.
The following examples illustrate the present invention
without however limiting the scope thereof. In these
35 examples, the parts and the percentages are by weight,
unless otherwise indicated.
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Exainple 1: Test of neutralization
The neutralizing capacity is evaluated by determining
the weight of amine (in grams) necessary for
5 neutralizing 100 g of oleic acid. In this example, the
neutralizing capacities of the following products are
compared:
• Amine (1) alone: monoethanolamine (MEoA);
• Amine (2) alone: n-heptyldiethanolamine
10 (C7DE0A);
• Mixture of amine (1) + amine (2): 70% by weight
of MEoA + 30% by weight of C7DE0A.
The results are presented in table 1 below:
15
Table 1
Amount necessary for
neutralizing 100 g of oleic
acid (g)
MEoA 6^^8
C7DE0A 36
MEoA (70%) + C7DE0A (30%) I 8_^^
Despite an observed neutralizing capacity that is much
lower for C7DE0A, it is observed that the mixture of
20 MEoA (70%) + C7DE0A (30%) retains a very good
neutralizing capacity owing to the provision of MEoA.
Exaicqple 2: Test of solubility in water
25 In this example, the following two amines are
considered:
• Amine (1) alone: methyldiethanolamine (MDEoA);
• Amine (2) alone: n-heptyldiethanolamine
(C7DE0A).
30
The appended figure 1 represents a ternary phase
diagram between these 2 amines and water. The
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percentages are expressed by weight. The miscible
mixtures are denoted by points (•) , the immiscible
mixtures are denoted by crosses (X).
5 The CvDEoA/water binary mixture is not miscible in all
proportions. There is immiscibility when the C7DE0A is
found in an amount of greater than 50%. In the area of
immiscibility (amount of C7DE0A greater than 50%), the
MDEoA acts as a coupling agent (co-solvent) when it is
10 present in a content of greater than 15%.
Example 3: Test of bacterial prolxferation
A test is carried out in order to evaluate the
15 bactericidal and/or bacteriostatic activity of a sample
of the composition of the invention, according to the
standard NF EN 1040 (April 2006).
A sample of a composition as it is (maximum
20 concentration of the test: 80%) and/or diluted with
water is added to a test suspension of bacteria
{Pseudomonas aeruginosa and Staphylococcus aureus). The
mixture is maintained at 20°C for 5 minutes.
25 An aliquote portion is removed at the end of this
contact time; the bactericidal and/or bacteriostatic
activity in this withdrawal is immediately neutralized
or suppressed according to a validated method. The
method used preferably is the dilution-neutralization
30 method. Filtration over a membrane is used when it is
not possible to find a suitable neutralizer.
The surviving bacteria in each sample are counted,
which makes it possible to calculate the degree of
35 reduction, denoted by "+" (low degree of reduction) to
"++++" (high degree of reduction) in table 2 below:
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Table 2
Cowposition Degree of redaction
MEoA +
C7DE0A ++++
MEoA (70%) + CiDEoA (30%) +++
MEoA (90%) + C7DE0A (10%) I ++

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CLAIMS
1. A biostatic neutralizing composition for aqueous
fluids comprising at least one organic or mineral base
5 (B) and at least one amine of formula (2):
["'"'••'•OH
R OH ^2)
wherein R^ represents a linear or branched hydrocarbon-
10 based radical, preferably a linear or branched alkyl
radical, having 7, 8, 9, 10, 11 or 12 carbon atoms.
2. The composition as claimed in claim 1, wherein the
base (B) is chosen from alkali metal hydroxides or
15 alkaline-earth metal hydroxides, nitrogenous bases,
preferably bases comprising at least one amine group,
more preferably 1 amine group.
3. The composition as claimed in claim 1 or claim 2,
20 wherein the base (B) is an organic base, quite
preferably the base (B) is an amine having a total
number of carbon atoms of less than or equal to 10,
preferably a total number of carbon atoms of less than
or equal to 9, optionally having 1 hydroxyalkyl radical
25 or 2 hydroxyalkyl radicals, or even 3 hydroxyalkyl
radicals, preferably 1 or 2, or even 3 hydroxyethyl
radicals, more preferably 1 or 2 hydroxyethyl radicals,
more preferably still 2 hydroxyethyl radicals.
30 4. The composition as claimed in any one of the
preceding claims, comprising at least one amine having
a total number of carbon atoms of less than 10,
preferably of less than 9, preferably at least one
amine of formula (1) and at least one amine of formula
35 (2):
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N k
^ ^ (1) ^ "" {2)
formula (1) and formula (2), wherein:
5 • either R''' represents a linear or branched
hydrocarbon-based radical, preferably a linear or
branched alkyl radical, having 1, 2, 3, 4, 5 or 6
carbon atoms, and R^ and R'' each represent the
radical - (CH2-CH2)-OH,
10 • or R""" represents a hydrogen atom and R^ represents
a hydrogen atom and R'' represents the radical
-(CH2-CH2)-OH,
• and, in both the- above cases, R^ represents a
linear or branched hydrocarbon-based radical,
15 preferably a linear or branched alkyl radical,
having 7, 8, 9, 10, 11 or 12 carbon atoms.
5. The composition as claimed in any one of the
preceding claims, wherein the amine of formula (1) is
20 chosen from butylamine, hexylamine, (2-ethyl)-
hexylamine,- monoethanolamine (MEA) ,
methyldiethanolamine (MDEoA), ethyldiethanolamine
(EDEoA), propyldiethanolamine (PrDEoA),
butyldiethanolamine (BDEoA), pentyldiethanolamine
25 (PDEoA) and hexyldiethanolamine (HDEoA), preferably
from monoethanolamine (MEA) and methyldiethanolamine
(MDEoA).
6. The composition as claimed in any one of the
30 preceding claims, wherein the amine of formula (2) is
chosen from n-heptyldiethanolamine (CiDEoA),
n-octyldiethanolamine (CsDEoA), 2-(ethyl)hexyldiethanolamine
(C2-6DE0A) , n-decyldiethanolamine
(CioDEoA) , n-undecyldiethanolamine (CuDEoA) and nwo
2012/045958 PCT/FR2011/052252
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dodecyldiethanolamine (C12DE0A), preferably the amine of
formula (2) is n-heptyldiethanolamine (C7DE0A).
7. The composition as claimed in any one of the
5 preceding claims, comprising at least one first amine
chosen from monoethanolamine (MEA), (2-ethyl)hexylamine
and methyldiethanolamine (MDEoA) and at least one
second amine which is n-heptyldiethanolamine {C7DE.0A) .
10 8. The composition as claimed in any one of the
preceding claims, comprising monoethanolamine (MEA) and
n-heptyldiethanolamine (C7DE0A) or methyldiethanolamine
(MDEoA) and n-heptyldiethanolamine (C7DE0A).
15 9. The composition as claimed in any one of the
preceding claims, wherein the base (B)/amine (2) molar
ratio, and in particular the amine (1)/amine (2) molar
ratio, is between 1:99 and 99:1, preferably between 1:9
and 9:1.
20
10. The composition as claimed in any one of the
preceding claims, in concentrated form or diluted in
water or in a water-soluble organic solvent or else in
an agueous-organic solvent, in any proportions.
25
11. The use, as a biostatic neutralizing additive, of
a composition as claimed in any one of claims 1 to 10,
for an industrial aqueous fluid.
30 12. The use as claimed in claim 11, wherein the
industrial aqueous fluid is an aqueous or aqueousorganic
white paint base, an aqueous pigment
concentrate, an aqueous dispersion of mineral fillers,
a metal working fluid, and others.
35
13. An industrial aqueous fluid comprising at least
one biostatic neutralizing composition as claimed in
any one of claims 1 to 10.
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14. The fluid as claimed in claim 13, comprising
between 0.0001 and 10% by weight, preferably between
0.001% and 5% by weight, of at least one biostatic
5 neutralizing composition as claimed in any one of
claims 1 to 9. ,
15. The industrial aqueous fluid as claimed in claim
13 or claim 14, which is an aqueous or aqueous-organic
10 white paint base, an aqueous pigment concentrate, an
aqueous dispersion of mineral fillers, a metal working
fluid, and others.