The invention relates to the field of preparing aqueous dispersions of organic, organometallic or inorganic particles. In particular, the invention relates to the preparation of aqueous suspensions comprising organic, organometallic or inorganic particles and at least one particular copolymer obtained by polymerization of at least one acid and at least one compound or at least one ester derived from a particular acid, in the presence of water, at least one initiator compound and at least one activator compound, followed by total or partial neutralization by means of at least one compound chosen from alkali metal hydroxides, alkaline earth metal hydroxides, alkaline earth metal dihydroxides and mixtures thereof. The invention relates to such a particular copolymer having a low polydispersity index and weight-average molecular weight, the preparation process thereof and the use thereof, especially for the preparation of an aqueous paint composition.

Description

9 parts

›The invention relates to the field of the…

The invention relates to the field of the preparation of aqueous dispersions of organic, organometallic or inorganic particles. In particular, the invention relates to the preparation of aqueous slurries comprising organic, organometallic or inorganic particles and at least one specific copolymer obtained by polymerization of at least one acid and of at least one compound or of at least one ester which are derived from a specific acid, in the presence of water, of at least one initiating compound and of at least one activating compound, followed by the complete or partial neutralization by means of at least one compound chosen from alkali metal hydroxides, alkaline earth metal hydroxides, alkaline earth metal dihydroxides and their mixtures. The invention relates to such a specific copolymer having low polydispersity indices (I p ) and weight-average molecular weight (M W ), to its process of preparation and to its use, in particular in the preparation of a water-based paint composition.

Water-soluble copolymers of use as dispersing agent during the preparation of slurries of particles are known. In particular, dispersing agents for the preparation of gloss paint compositions comprising dispersed titanium dioxide particles are known.

For such paint compositions, qualities of gloss of the coating obtained after application are generally desired. Very good optical properties as well as very good mechanical properties are also desired.

Processes for the preparation of acrylic acid and ester copolymers which employ sodium thiosulfate are known; for example, CN 101884888 discloses such grinding agents. JP 1986-53627 discloses the corrosion-inhibiting properties of a copolymer comprising sulfonic groups. EP 2 657 261 describes an acrylic acid homopolymer.

Known copolymers prepared by means of sulfites have to be prepared in a highly diluted manner, for example, at a solids content of 7% to 12% by weight, in order to prevent the formation of an insoluble precipitate during the neutralization thereof with sodium hydroxide or with potassium hydroxide. Neutralization with ammonia then constitutes the only alternative, despite the inconveniences which result therefrom.

Generally, the dispersing agents of the state of the art are prepared by processes comprising a stage of neutralization by means of ammonia, thus improving the dispersing properties of the copolymer obtained. The choice of this specific neutralization agent can also influence the optical properties of the paint coating subsequently produced. It can also influence the mechanical properties of this coating.

For example, U.S. Pat. No. 3,859,260 describes a redox radical polymerization reaction which employs an initiating compound and a large amount of bisulfite as reducing agent. The polymer is neutralized with potassium hydroxide or with ammonia.

U.S. Pat. No. 4,102,843 describes an aqueous emulsion paint composition comprising an alkyl acrylate and acrylic acid copolymer as dispersing agent. This copolymer is obtained by polymerization in isopropanol and of an initiating compound and then it is neutralized by means of sodium hydroxide.

However, during the implementation of known processes, the residual presence of more or less large amounts of ammonia can cause problems of odor, of health or of industrial hygiene.

Moreover, the presence of volatile organic compounds (VOCs), such as ammonia, in paint compositions is also problematic.

Thus, apart from the properties of good dispersion of the particles and of improved optical properties, the dispersing agents also have to make it possible to prevent or reduce the presence of volatile organic compounds. In particular, such dispersing agents should not result in the release of ammonia.

One solution to this problem could consists in employing neutralization agents while avoiding the presence of ammonia. However, the use of alkali metal cations generally results in a deterioration in the dispersing properties or optical properties desired. In particular, some sulfonated polymers obtained by a polymerization reaction catalyzed by peroxide and bisulfite prove to be difficult or impossible to neutralize by means of alkali metal derivatives as a result of the risk of precipitation in the prepared compositions of salts of these alkali metals, in particular alkali metal sulfates.

It is also necessary to have available preparation methods during which the solids concentration of the reaction medium has to be high while making it possible to avoid the use of ammonia during the neutralization of the polymers prepared. Concentrations of greater than 20% by weight or else of greater than 30% or greater than 40% or 45% by weight are particularly preferred.

Furthermore, the dispersing agents used during the preparation of slurries of particles, and in particular of slurries of particles for the preparation of paint compositions, have to make it possible to maintain or improve the abrasion resistance or to improve the wet abrasion resistance.

These dispersing agents also have to maintain or improve the shelf life as well as the flow and the leveling. The maintenance or the improvement in the hiding power should also be desired. Pigment compatibility and blocking resistance, in other words the resistance to the adhesion of two coating layers brought into contact, are also properties desired for the coatings prepared. For these coatings, an improvement in the resistance to stains is also desired.

An important property also resides in the stability of the paint compositions during their storage in containers.

The dispersing agents for particles also have to have satisfactory or improved intrinsic properties, in particular a low viscosity. They should also be widely compatible with different types of particles or with different types of materials or of additives. They should thus be very versatile.

Furthermore, the copolymers of use as dispersants, in particular as dispersants of acrylic type for a water-based paint composition, have to be able to be prepared in high concentrations which are advantageous commercially, in particular in concentrations of greater than 35% by weight of neutralized copolymer of the solution.

›There thus exists a need for a person…

There thus exists a need for a person skilled in the art to have available dispersing agents for particles having improved properties.

The invention makes it possible to provide a solution to all or some of the problems encountered with the dispersing agents of the state of the art.

Thus, the invention provides a copolymer obtained according to a process comprising:

at least one polymerization reaction:

(a) of at least one acid chosen from acrylic acid, methacrylic acid and their mixtures; and (b) of at least one compound or of at least one ester of a compound which are derived from an acid chosen from acrylic acid, methacrylic acid, itaconic acid and maleic acid; in the presence of water, of at least one initiating compound chosen from hydrogen peroxide, sodium persulfate, potassium persulfate, ammonium persulfate and their mixtures and of at least one activating compound chosen from alkali metal hypophosphites, in particular sodium hypophosphite, potassium hypophosphite, and their mixtures, and preferably in the absence of sodium thiosulfate;

the complete or partial neutralization by means of at least one compound chosen from MgO, CaO, alkali metal hydroxides, alkaline earth metal hydroxides, alkaline earth metal dihydroxides and their mixtures.

Advantageously, the invention provides a copolymer, the intrinsic characteristics of which can be controlled. Preferably according to the invention, the copolymer obtained has a weight-average molecular weight (M W ) ranging from 1000 to 6000 g/mol, preferably from 1500 to 4000 g/mol. Also preferably according to the invention, the copolymer obtained has a polydispersity index (I p ) ranging from 1.5 to 3, preferably from 1.8 to 2.3.

According to the invention, the neutralization is carried out after the polymerization reaction. The invention thus also provides an alkali metal salt or an alkaline earth metal salt of a copolymer obtained according to the invention or else a mixture of such a salt and of a copolymer obtained according to the invention.

Preferably according to the invention, the polymerization reaction employs an acid (a) chosen from acrylic acid, methacrylic acid and their mixtures. Acrylic acid is preferred. Apart from acrylic acid and methacrylic acid, the polymerization reaction can employ at least one other acid (a). Preferably, the polymerization reaction then also employs another acid (a) chosen from acrylic acid, methacrylic acid, itaconic acid and maleic acid. Advantageously, the polymerization reaction can employ acrylic acid with itaconic acid or with maleic acid or else methacrylic acid with itaconic acid or with maleic acid.

Also preferably according to the invention, the polymerization reaction employs from 10% to 90%, preferably from 30% to 60%, by weight of compound (a), with respect to the total amount by weight of compounds (a) and (b).

Preferably according to the invention, the polymerization reaction employs at least one compound (b) which is a compound of formula (A):

in which:

X, which is identical or different, independently represents a linear or branched C 1 -C 10 -alkylene group; n represents a whole or decimal number ranging from 1 to 5; Q represents a group chosen from C(O), CH 2 , CH 2 —O and (CH 2 ) 4 —O; L represents a direct bond or a CH 2 group; R 1 represents H, CH 3 or C(O)OH; R 2 represents H or C(O)OH.

Also preferably according to the invention, the polymerization reaction employs at least one compound (b) of formula (I), (II), (III) or (IV):

in which:

X, which is identical or different, independently represents a linear or branched C 1 -C 10 -alkylene group; n represents a whole or decimal number ranging from 1 to 5; L represents a direct bond or a CH 2 group; R 1 represents H, CH 3 or C(O)OH; R 2 represents H or C(O)OH.

More preferably, the compound (b) is a compound of formula (A), (I), (II), (III) or (IV) in which X, which is identical or different, independently represents a linear or branched C 2 -C 4 -alkylene group, in particular an ethylene group, a propylene group or a butylene group.

More preferably still, the compound (b) is a compound of formula (A), (I), (II), (III) or (IV) in which:

L represents a direct bond, R 1 represents H and R 2 represents H; or L represents a direct bond CH 2 , R 1 represents CH 3 and R 2 represents H; or L represents a direct bond, R 1 represents H and R 2 represents C(O)OH; or L represents a CH 2 group, R 1 represents C(O)OH and R 2 represents H.

Much more preferably, the compound (b) is a compound of formula (A), (I), (II), (III) or (IV) in which n represents 1 and:

in particular a compound of formula (A), (I), (II), (III) or (IV) in which n represents 1 and:

L represents a direct bond, R 1 represents H and R 2 represents H; or L represents a direct bond CH 2 , R 1 represents CH 3 and R 2 represents H.

Particularly preferably according to the invention, the polymerization reaction employs a compound (b) chosen from hydroxyethyleneoxy acrylate, hydroxypropyleneoxy acrylate, hydroxyethyleneoxy methacrylate or hydroxypropyleneoxy methacrylate. Hydroxypropyleneoxy acrylate or 2-hydroxypropylacrylate (CAS 999-61-1) is preferred. Also preferably according to the invention, the polymerization reaction employs from 10% to 90%, preferably from 40% to 70%, by weight of compound (b), with respect to the total amount by weight of compounds (a) and (b).

According to the invention, the polymerization reaction is carried out in the presence of water, of at least one initiating compound and of at least one activating compound. The preferred initiating compound is hydrogen peroxide (H 2 O 2 ), which can be combined with metal salts, in particular iron salts, copper salts or their mixtures. The preferred activating compound is sodium hypophosphite (NaPO 2 H 2 ). Preferably according to the invention, the polymerization reaction employs from 5% to 15% by weight, preferably from 7% to 11% by weight, of alkali metal hypophosphites, with respect to the total amount by weight of monomers.

›Preferably according to the invention, the complete or…

Preferably according to the invention, the complete or partial neutralization is carried out by means of at least one compound chosen from NaOH, KOH, MgO, CaO, Mg(OH) 2 , Ca(OH) 2 and their mixtures. Advantageously, the partial neutralization is carried out by means of NaOH, KOH, MgO, CaO, Mg(OH) 2 , Ca(OH) 2 and their mixtures and the complete neutralization is carried out by means of NaOH, KOH and their mixtures. Particularly preferably according to the invention, the complete or partial neutralization is carried out by means of potassium hydroxide or sodium hydroxide and in particular by means of potassium hydroxide.

Advantageously according to the invention, the initiating compound can be chosen from hydrogen peroxide, sodium persulfate, potassium persulfate, ammonium persulfate and their mixtures and the neutralization can be carried out by means of potassium hydroxide.

Apart from a specific copolymer, the invention also relates to a process for the preparation of this copolymer. The process according to the invention comprises:

at least one polymerization reaction:

For the process according to the invention, the polymerization reaction can be repeated. The neutralization is then carried out after the polymerization reaction. The invention thus also provides a process for the preparation of an alkali metal salt or of an alkaline earth metal salt of a copolymer obtained according to the process of the invention or else a mixture of such a salt and of a copolymer obtained according to the process of the invention.

A preferred process according to the invention employs an acid (a) chosen from acrylic acid, methacrylic acid and their mixtures. Acrylic acid is preferred. Apart from acrylic acid and methacrylic acid, the polymerization reaction can employ at least one other acid (a). Preferably, the polymerization reaction then also employs another acid (a) chosen from acrylic acid, methacrylic acid, itaconic acid and maleic acid. Advantageously, the polymerization reaction can employ acrylic acid with itaconic acid or with maleic acid or else methacrylic acid with itaconic acid or with maleic acid.

A process which is also preferred according to the invention employs from 10% to 90%, preferably from 30% to 60%, by weight of compound (a), with respect to the total amount by weight of compounds (a) and (b).

A preferred process according to the invention employs at least one compound (b) which is a compound of formula (A):

in which:

A process which is also preferred according to the invention employs at least one compound (b) which is a compound of formula (I), (II), (III) or (IV):

in which:

More preferably for the process according to the invention, the compound (b) is a compound of formula (A), (I), (II), (III) or (IV) in which X, which is identical or different, independently represents a linear or branched C 2 -C 4 -alkylene group, in particular an ethylene group, a propylene group or a butylene group. More preferably still, the compound (b) is a compound of formula (A), (I), (II), (III) or (IV) in which:

L represents a direct bond, R 1 represents H and R 2 represents H; or L represents a direct bond, R 1 represents CH 3 and R 2 represents H; or L represents a direct bond, R 1 represents H and R 2 represents C(O)OH; or L represents a CH 2 group, R 1 represents C(O)OH and R 2 represents H.

Much more preferably, the compound (b) is a compound of formula (A), (I), (II), (III) or (IV) in which n represents 1 and:

in particular a compound of formula (A), (I), (II), (III) or (IV) in which n represents 1 and:

L represents a direct bond, R 1 represents H and R 2 represents H; or L represents a direct bond, R 1 represents CH 3 and R 2 represents H.

A process which is also preferred according to the invention employs from 10% to 90%, preferably from 40% to 70%, by weight of compound (b), with respect to the total amount by weight of compounds (a) and (b).

For the process according to the invention, the polymerization reaction is carried out in the presence of water, of at least one initiating compound and of at least one activating compound. The preferred initiating compound is hydrogen peroxide (H 2 O 2 ), which can be combined with metal salts, in particular iron salts, copper salts or their mixtures. The preferred activating compound is sodium hypophosphite (NaPO 2 H 2 ). Preferably according to the invention, the polymerization reaction employs from 5% to 15% by weight, preferably from 7% to 11% by weight, of alkali metal hypophosphites, with respect to the total amount by weight of monomers.

›Apart from a specific copolymer and a process…

Apart from a specific copolymer and a process for the preparation of this copolymer, the invention also relates to the use of this copolymer.

Preferably, the invention relates to the use of at least one copolymer according to the invention in the preparation of an aqueous dispersion, in particular in the preparation of an aqueous dispersion of organic, organometallic or inorganic particles.

The invention thus provides a specific aqueous dispersion comprising at least one copolymer according to the invention and organic, organometallic or inorganic particles dispersed in an aqueous medium, preferably dispersed in water.

Preferably, the particles employed according to the invention are particles of at least one pigment. Also preferably, the particles employed according to the invention are inorganic particles. Particularly preferably, they are TiO 2 particles.

Among aqueous dispersions, the invention preferably provides an aqueous slurry comprising organic, organometallic or inorganic particles and at least one copolymer according to the invention within an aqueous substrate, preferably in water.

The copolymer according to the invention, the aqueous dispersion according to the invention or the aqueous slurry according to the invention can be used in the preparation of numerous compositions. Preferably, the copolymer according to the invention, the aqueous dispersion according to the invention or the aqueous slurry according to the invention are used in the preparation of an aqueous adhesive composition or of an aqueous coating composition, in particular of a thick-layer coating or of a thin-layer coating.

Particularly preferably according to the invention, the aqueous coating composition is an aqueous varnish composition or paint composition, for example a decorative paint or industrial paint composition.

Thus, preferably, the invention also provides a water-based paint composition comprising, in an aqueous substrate, preferably in water,

at least one film-forming copolymer latex; at least one organic or inorganic pigment; at least one copolymer according to the invention.

The specific, advantageous or preferred characteristics of the copolymer according to the invention make it possible to define specific, advantageous or preferred aqueous dispersions according to the invention, specific, advantageous or preferred aqueous slurries according to the invention and specific, advantageous or preferred compositions according to the invention.

The examples which follow make it possible to illustrate the different aspects of the invention.

›Examples5

›EXAMPLE 1

Process (1) for the Preparation of Copolymers According to the Invention

The following are weighed into a 1000 ml glass reactor equipped with a mechanical stirring system and with a heating system of oil bath type:

310 grams of water, 0.134 g of iron sulfate heptahydrate, 0.02 g of copper sulfate pentahydrate.

The combined mixture is then heated to 95° C.±2° C. and the following reactants are then added using three peristaltic pumps with continuous additions over two hours at 95° C.:

Pump 1: the monomers:

acrylic acid: 284.04 g 2-hydroxypropyleneoxy acrylate: 180 g water: 31.6 g

Pump 2: the initiating compound:

130-volume aqueous hydrogen peroxide solution: 37 g water: 45 g

Pump 3: the reducing activating compound:

50% sodium hypophosphite solution: 96 g.

After rinsing the pumps, the combined mixture is subsequently heated at 95° C. for 45 min.

A polymer is obtained which is then analyzed:

residual monomers: acrylic acid=30 ppm and 2-hydroxypropyl acrylate<60 ppm, M W =2795 g/mol, I p =2.

This polymer is subsequently neutralized at pH=8±0.5 in two forms and for a solids content of 45%±0.5%:

neutralization with sodium hydroxide in order to obtain the copolymer 1-1, neutralization with potassium hydroxide in order to obtain the copolymer 1-2.

›EXAMPLE 2

Process (2) for the Preparation of Comparative Copolymers

The following are weighed into a 1000 ml glass reactor equipped with a mechanical stirring system and with a heating system of oil bath type:

310 grams of water, 0.134 g of iron sulfate heptahydrate, 0.02 g of copper sulfate pentahydrate.

The combined mixture is then heated to 95° C.±2° C. and the following reactants are then added using three peristaltic pumps with continuous additions over two hours at 95° C.:

Pump 1: the monomers:

acrylic acid: 284.04 g 2-hydroxypropyleneoxy acrylate: 180 g water: 31.6 g

Pump 2: the initiating compound:

130-volume aqueous hydrogen peroxide solution: 37 g water: 45 g

Pump 3: the reducing activating compound:

50% sodium hypophosphite solution: 96 g.

After rinsing the pumps, the combined mixture is subsequently heated at 95° C. for 45 min. A polymer is obtained which is then analyzed:

residual monomers: acrylic acid=30 ppm and 2-hydroxypropyl acrylate<60 ppm, M W =2755 g/mol, I p =3.

This polymer is subsequently neutralized at pH=8±0.5 and for a solids content of 45%±0.5% by neutralization with ammonia in order to obtain the copolymer 2-1.

›EXAMPLE 3

Process (3) for the Preparation of Comparative Copolymers

The following are weighed into a 1000 ml glass reactor equipped with a mechanical stirring system and with a heating system of oil bath type:

180 grams of water, 0.003 g of iron sulfate heptahydrate.

The combined mixture is then heated to 73° C.±2° C. and the following reactants are then added using three peristaltic pumps with continuous additions over two hours at 73° C.:

Pump 1: the monomers:

acrylic acid: 245 g 2-hydroxypropyleneoxy acrylate: 159.89 g water: 60 g

Pump 2: the initiating compound:

ammonium persulfate: 5.88 g water: 60 g

Pump 3: the reducing activating compound:

40% sodium bisulfite solution: 142 g.

The monomers and the reducing compound are added over 3 h 30 min; the initiating compound is added over 3 h 35 min. After rinsing the pumps, the combined mixture is subsequently heated at 73° C. for 60 min. A polymer is obtained which is then analyzed:

residual monomers: acrylic acid=60 ppm and 2-hydroxypropyl acrylate<60 ppm, M W =3115 g/mol, I p =2.4.

This polymer is subsequently neutralized at pH=8±0.5 in two forms and for a solids content of 45%±0.5%:

neutralization with sodium hydroxide in order to obtain the copolymer 3-1, neutralization with potassium hydroxide in order to obtain the copolymer 3-2.

›EXAMPLE 4

Process (4) for the Preparation of Comparative Copolymers

The following are weighed into a 1000 ml glass reactor equipped with a mechanical stirring system and with a heating system of oil bath type:

180 grams of water, 0.003 g of iron sulfate heptahydrate.

The combined mixture is then heated to 73° C.±2° C. and the following reactants are then added using three peristaltic pumps with continuous additions over two hours at 73° C.:

Pump 1: the monomers:

acrylic acid: 245 g 2-hydroxypropyleneoxy acrylate: 159.89 g water: 60 g

Pump 2: the initiating compound:

ammonium persulfate: 5.88 g water: 60 g

Pump 3: the reducing activating compound:

40% sodium bisulfite solution: 142 g.

residual monomers: acrylic acid=60 ppm and 2-hydroxypropyl acrylate<60 ppm, M W =2640 g/mol, I p =2.1.

This polymer is subsequently neutralized at pH=8±0.5 and for a solids content of 45%±0.5% by neutralization with ammonia in order to obtain the copolymer 4-1.

The molecular weights of the copolymers are determined by size exclusion chromatography (SEC) or gel permeation chromatography (GPC). This technique employs a Waters brand liquid chromatography device provided with a detector. This detector is a Waters brand refractometric concentration detector. This liquid chromatography equipment has a size exclusion column in order to separate the different molecular weights of the copolymers studied. The liquid elution phase is an aqueous phase adjusted to pH 9.00 using 1N sodium hydroxide containing 0.05M of NaHCO 3 , 0.1M of NaNO 3 , 0.02M of triethanolamine and 0.03% of NaN 3 .

According to a first stage, 0.9% of the copolymer solution on a dry basis is diluted in the dissolution solvent of the SEC, which corresponds to the liquid elution phase of the SEC, to which is added 0.04% of dimethylformamide, which acts as marker of flow rate or internal standard. Filtration is then carried out using a 0.2 μm filter. 100 μl are subsequently injected into the chromatography device (eluent: an aqueous phase adjusted to pH 9.00 with 1N sodium hydroxide containing 0.05M of NaHCO 3 , 0.1M of NaNO 3 , 0.02M of triethanolamine and 0.03% of NaN 3 ).

The liquid chromatography device contains an isocratic pump (Waters 515), the flow rate of which is adjusted to 0.8 ml/min. The chromatography device also comprises an oven which itself comprises, in series, the following system of columns: a precolumn of Waters Ultrahydrogel Guard Column type with a length of 6 cm and an internal diameter of 40 mm, and a linear column of Waters Ultrahydrogel type with a length of 30 cm and an internal diameter of 7.8 mm. The detection system is composed of a Waters 410 refractometric detector of RI type. The oven is brought to a temperature of 60° C. and the refractometer is brought to a temperature of 45° C.

The chromatography device is calibrated by means of powdered sodium polyacrylate standards of different molecular weights certified by the supplier: Polymer Standard Service or American Polymer Standards Corporation.

The characteristics of the copolymers prepared are presented in table 1.

During the implementation of the process (1), solutions which are clear and stable on storage are obtained. During the implementation of the process (2), only the polymer neutralized with ammonia is clear.

Thus, the polymerization according to the invention, which employs an initiating compound of sodium hypophosphite type, makes it possible to obtain copolymers of use as acrylic dispersants, with high and commercially advantageous concentrations (>35%, indeed even than 40% or else than 43%, for example) and with alkali metal cations resulting from the neutralization.

It is not possible to obtain such results when the reducing initiating compound is sodium bisulfite, unless ammonia is used during the neutralization of the copolymer, then resulting in the presence of a release of volatile organic compounds during the use of these polymers.

›EXAMPLE 5

Use of the Copolymers in the Preparation of Paint Compositions and Evaluation of the Properties of the Paint

Three paint formulations are prepared by mixing the constituents presented in table 2.

The Stormer viscosity (KU) (ASTM D 562), the ICI viscosity (ASTM D 4287) and the Brookfield viscosity (ASTM D 2196) at 10 revolutions/min and 100 revolutions/min at 25° C. were measured for the three paint formulations. The results are presented in table 3.

The dispersing properties of the copolymers employed were evaluated by producing deflocculation curves for different grades of TiO 2 particles. The effectiveness of the dispersing agent during the suspending in water of titanium dioxide at a specific concentration is thus demonstrated.

An aqueous TiO 2 slurry is prepared by introducing 190 g of water into a beaker, by then adding 612 g of rutile TiO 2 (Kronos 2310, Tronox CR 828 and DuPont Ti-Pure R 902) and by slowly mixing by means of a mechanical mixer until complete homogenization is achieved. A thick paste is formed, the solids content of which is confirmed by means of a balance when dry. The solids content has to be 76.5±0.5%.

The initial Brookfield viscosity (ASTM D 2196) of the thick paste is measured at 100 rev/min.

A first amount of dispersing agent is then added and mixing is carried out for 5 min in order to obtain a dispersion of the TiO 2 particles.

Brookfield viscosity (ASTM D 2196) of the thick paste comprising the dispersing agent is measured at 100 rev/min.

The stages of addition of slightly increasing amounts of dispersing agent, of mixing and of measuring the viscosity are repeated until, at one measurement, a viscosity value which is stabilized or which varies very slightly is obtained. The results for the different rutile TiO 2 products Kronos 2310, Tronox CR 828 and DuPont Ti-Pure R 902 are presented in tables 4, 5 and 6.

The different copolymers make possible good dispersion of the TiO 2 particles of different grades.

The optical properties of the three paint formulations were also evaluated by measuring their gloss at 20°, at 60° and at 85° by means of a Micro-Tri-Gloss reflectometer from BYK-Gardner (ASTM D3928) and their opacifying properties (ASTM D2805). The measurements were carried out 24 hours after application of the paint.

The flow-sagging compromise of these three formulations was also evaluated (respectively ASTM D4400 and ASTM D4062).

The clearness index or whiteness index of the paint film was also measured by the measurement of the L* component in the Lab (L*a*b*) colorimetric space, using a spectrophotometer (ASTM D2244).

The wet abrasion resistance of these three formulations was also evaluated (ASTM D2486 and ASTM D4213).

The combined results are presented in table 7.

The neutralized copolymers according to the invention make possible good performance qualities of dispersion of the TiO 2 particles as well as very good optical properties and excellent wet abrasion resistance properties for the water-based paint formulations prepared.

›Tables in the description — 7

TABLE 1 — Copolymer

	According to the invention	Comparative
	1-1	1-2	2-1	3-1	3-2	4-1
M w (g/mol)	2795	2795	2755	3115	3115	2640
I p	2	2	3	2.4	2.4	2.1
Specific viscosity	0.320	0.320	0.337	0.273	0.327	0.327
Appearance after	clear	clear	clear	cloudy	phase-	clear
neutralization					separated

TABLE 2 — Amount

	Composition	(kg)
Pasting phase
Water		37.78
Sequestering agent	Potassium tripolyphosphate (KTPP)	0.45
Dispersing copolymer	according to the invention	2.09
1-1, 1-2 or 2-1	or comparative
Surface-active agent	Triton CF-10	1.36
Antifoaming agent	Rhodaline 640	0.45
Fungicide	Karhon LX (1.5%)	0.68
Sodium carbonate	Aldrich	1.91
Rutile TiO 2 (76.5% by	Kronos 2310/Tronox CR 828/Ti-Pure R	112.49
weight)	902
Kaolin	Polygloss 90	9.07
Water		38.28
Remainder
Latex	Arkema Encor 300	158.76
Latex	Arkema Encor 626	68.04
Antifoaming agent	Rhodaline 640	0.91
Thickening agent	Coatex Rheotech 2800	9.84
Thickening agent	Coatex Rheotech 4800	0.18
Water		44.45
TOTAL	486.75

TABLE 3 — Dispersing copolymer

	1-1	1-2	2-1
Stormer (KU)	112.2	117.2	113.2
ICI	0.555	0.495	0.475
Brookfield 10 rev/min	9560	14 600	10 400
(mPa · s)
Brookfield 100 rev/min	3715	4300	3660
(mPa · s)

TABLE 4

	Amount of	%	Brookfield viscosity
TiO 2	dispersant	(dry/dry)/	100 rev/min
Kronos 2310	(g)	TiO 2	(mPa · s)
Dispersing	1	0.060	19 360
copolymer 1-1	1.2	0.073	14 240
	1.4	0.083	11 680
	1.6	0.098	3800
	1.9	0.117	638
	2.2	0.132	208
	2.5	0.148	174.4
	2.9	0.176	181.4
	3.5	0.212	286.2
Dispersing	1.0	0.0637	18 920
copolymer 1-2	1.4	0.0892	9150
	1.7	0.1083	1260
	2.0	0.1274	235
	2.2	0.1401	180
	2.4	0.1528	162
	3.4	0.2165	118
Dispersing	1.0	0.0607	NA
copolymer 2-1	1.2	0.0728	17 920
	1.5	0.0910	12 480
	1.8	0.1092	5800
	2.0	0.1214	1700
	2.3	0.1396	392
	2.6	0.1578	214.4
	2.8	0.1699	185.6
	3.1	0.1881	177.6
	4.4	0.2670	348.8

TABLE 5

	Amount of	%	Brookfield viscosity
TiO 2	dispersant	(dry/dry)/	100 rev/min
Tronox CR 828	(g)	TiO 2	(mPa · s)
Dispersing	1.5	0.092	not measurable
copolymer 1-1	1.7	0.104	12 720
	1.9	0.116	29 360
	2.2	0.133	19 680
	2.5	0.152	23 520
	3.3	0.203	10 320
	3.6	0.219	5230
	3.9	0.238	3280
	4.2	0.258	1284
	4.6	0.284	604
	4.9	0.297	548
	5.3	0.324	454
	5.82	0.356	491
Dispersing	2.7	0.170	15 000
copolymer 1-2	3.1	0.195	14 200
	3.4	0.214	13 560
	3.9	0.246	3180
	4.2	0.265	1644
	4.4	0.277	1034
	4.7	0.296	780
	4.9	0.309	592
	5.1	0.321	491
	5.3	0.324	431
	6.3	0.385	374
Dispersing	1.2	0.0731	31 880
copolymer 2-1	1.4	0.0852	27 980
	1.6	0.0974	27 680
	1.9	0.1157	27 400
	2.1	0.128	27 760
	3.3	0.201	11 040
	3.5	0.213	7280
	3.7	0.225	3160
	3.9	0.237	1246
	4.3	0.262	750
	4.5	0.274	534
	4.9	0.298	466
	5.10	0.311	376
	5.80	0.353	536

TABLE 6

	Amount of	%	Brookfield viscosity
TiO 2	dispersant	(dry/dry)/	100 rev/min
DuPont Ti-Pure R 902	(g)	TiO 2	(mPa · s)
Dispersing	2.06	0.126	18 320
copolymer 1-1	2.3	0.143	7960
	2.6	0.157	2890
	2.9	0.175	688
	3.1	0.191	408
	3.4	0.208	266
	3.7	0.227	275
	4.4	0.267	216.4
	4.8	0.293	229.2
Dispersing	2.2	0.140	18 600
copolymer 1-2	2.5	0.159	6560
	2.8	0.178	836
	3.0	0.191	490
	3.2	0.204	286
	3.4	0.216	228
	3.6	0.229	197
	4.5	0.286	152
Dispersing	1.7	0.1060	16 800
copolymer 2-1	2.1	0.1262	5880
	2.3	0.1408	1900
	2.5	0.1542	900
	2.7	0.165	480
	3.0	0.180	283.6
	3.3	0.201	238.8
	3.6	0.220	210
	4.0	0.242	204.8

TABLE 7 — Dispersing copolymer

	1-1	1-2	2-1
Gloss 20°	36.5	30.4	33.3
Gloss 60°	70.7	69.1	69.8
Gloss 85°	93.5	91.7	94.3
Opacity	97.37	96.98	97.38
Color L	95.4	95.38	95.25
Color a	−2.59	−2.58	−2.57
Color b	2.34	2.43	2.31
Flow	12	14	14
Sagging	7	7	7
Wet abrasion resistance (cycles)	349	742	503

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10 codes

IPC · International Patent Classification

Section C — Chemistry; metallurgy

C08F220/20
C09D5/02
C09D133/10
C09D7/45
C08F220/28
C09D133/06
C08K3/22
C08F220/06
C09D133/08
C09D133/02

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