A compound rheology modifier. The compound to urethane functions of the invention can be prepared by a multistep process which implement compounds isoeyanates different functions. For the preparation of the urethane compound according to the invention, a monoisocyanate compound, including a monoisocyanate compound from the separate condensation of unsymmetrical diisocyanate compound with a reactive compound, is reacted with an alkylene glycol compound in the presence of a polyisocyanate compound. The invention also provides coating compositions comprising inorganic particles and a urethane compound according to the invention.

Generally for aqueous coating compositions, particularly for the aqueous compositions of paint or varnish, it is necessary to control the viscosity as for low or medium shear rates as high shear gradients. Indeed, during its preparation, storage, application or drying, a paint formulation faces many pressures requiring particularly complex rhéoiogiques properties.

During storage of the paint, the pigment particles tend to settle by gravity, stabilize the dispersion of the pigment particles then requires the availability of a paint formulation having a viscosity high at very low shear rates corresponding to the speed limit of the particles.

The paint is taken the amount of paint carried by means of an application tool, a brush, a brush or a roller for example. The tool then plunged removed the paint bucket carrying a high amount of paint avoid having to be re-tempered more frequently. Painting taking is increasing function of viscosity. Calculating the equivalent shear rate is a function of the rate of flow of paint to a particular thickness of paint on the tool. The paint formulation should also have a high viscosity at low shear rates or means.

In addition, a high-build of the paint must be searched so that when applied to a substrate, a significant amount of paint to be deposited during each pass. A high build then affords a greater wet film during each passage of the tool A high viscosity of the paint formulation has to be searched at high shear gradients.

A high viscosity at high shear rates also reduce or eliminate the risk of éelaboussures or droplets forming during application of the pemture.

A reduced viscosity at low or medium shear rates also yield good appearance stretched after application of the paint, in particular a monocouehe paint, to a substrate including the coated surface then present a uniform appearance without unevenness or hollow. The final visual appearance of the dry film is so much better.

Moreover, after its deposit on a surface including a vertical surface, the paint should not form sag. It is then necessary that the pemture formulation has a high viscosity at low shear gradients and means,

Finally, after being deposited on a surface, the paint should have a significant leveling capacity. A reduced viscosity at low and medium shear gradients of the paint formulation is then required.

HEUR type compounds (hycirophobicaÎiy eîhoxylaled modified urethanes or urethane ethoxylated and hydrophobically modified) are known as rheological modifiers.

US 4,180,491 describes the preparation of various polyurethane compounds. In the preparation of these compounds, a first step comprises reacting a polyethylene glycol (PEG) with a monoisocvanate until the complete consumption of the isocyanate functions of monoisocvanate. Then, during a second stage, the condensate PEG-monoisocyanate, produced during the first step is reacted with a triisocyanate compound.

EP 2444432 and FR 2894980 describe urethane compounds and their use.

However, the known compounds HOUR will allow, not always provide a satisfactory solution. In particular, the rheology modifiers compounds of the prior art do not improve satisfactorily the compromise between Stormer viscosity (measured at low to medium shear rates, expressed in KU units) and ICI viscosity (measured at high or high shear rates and expressed in s "1 ). in particular, the rheology modifiers known compounds is not always possible to increase the ratio ICI viscosity / viseosité Stormer.

There is therefore a need for improved rheology modifiers.

The urethane compound rinvention provides a solution to all or part of the problems of rheology modifiers of the prior art.

Thus, the invention provides a urethane compound prepared in the absence of any compound diisocyanate by reacting:

(A) at least one monoisocyanate compound selected from:

(Al) a compound comprising a single isocyanate functional group and (A2) at least one monoisocyanate compound from the separated reaction

(A2-I) at least one compound comprising at least one labile hydrogen atom and

(A2-2) of at least one asymmetric diisocyanate compound,

(B) at least one isocyanate compound comprising more than two isocyanate functions, and

(C) at least one compound of formula (I):

(I)

wherein L represents independently a residue poly (alkylene glycol) and n represents a number from 40 to 400.

Preferably according to the invention, the condensation of the compounds (A), (B) and (C) is conducted in the presence of a catalyst. This catalyst may be selected from acetic acid, an amine, preferably l, 8-diazabicyelo [5.4, û] undec-7 ~ ene (DBU), a derivative of a metal selected from Al, Bi, Sn, Hg, Pb, Mn, Zn sZr, Ti. Traces of water can also participate in the catalysis of the reaction. Examples of metal compounds, preferred is a compound selected from dibutyltin dilaurate bismuth diacetate, dibutyl bismuth oxide, dibutyl bismuth, bismuth carboxylate, dibutyl tin dilaurate, dibutyl tin diacetate. dibutyltin oxide, a mercury derivative, a lead compound, zinc salts, manganese salts, a compound comprising zirconium chelate, a chelate compound comprising aluminum. The preferred metal compound is selected from a derivative of Bi and a compound of Sn.

Advantageously, the urethane compound according to the invention is a compound having a hydrophilic character, it may be formulated in an aqueous medium.

According to the invention, the monoisocyanate compounds (Al) and (A2) include only one isocyanate function. This is known reagents as such or prepared for the purpose of invention Thus, the compounds (Al) and (A2) include only one reactive isocyanate functionality in the reaction with the compounds (B) and (C), the reaction of these monoisocyanate compounds (Al) and (A2) with the compounds (B) and (C) is therefore performed in the absence of diisocyanate compound.

Preferably according to the invention, the monoisocyanate compound (IA) is a compound of formula (II):

R-NCO

(II)

wherein R represents a linear, branched or cyclic, saturated, unsaturated or aromatic, preferably a linear alkyl group, branched or cyclic containing from 6 to 20 carbon atoms or. linear alkenyl, branched or cyclic containing from 6 to 20 carbon atoms.

Also preferably according to the invention so, the monoisocyanate compound (Al) is a compound selected from:

» les composés monoisocyanates aromatiques, notamment phenyl isocyanate, diphenylmethane monoisocyanate, 2-phenylethyJ isocyanate, 4-tolyl isocyanate, 2-tolyl isocyanate, 2,5-dimethylphenyl isocyanate, 3,4-dimethylphenyî isocyanate, 2,3-dimethylphenyl isocyanate, 4-isocyanato-4'-methyld phenylmethane ;

"Aromatic monoisocyanates poîyf nctionnels compounds, including

2-methoxy-4-nitrophenyl. isocyanate, polymethylene polyphenyl isocyanate ; » les composés aîkyl-monoisocyanates, notamment hexyl-isocyanate, heptyi- isocyanate, octyl-isocyanate, n-nonyl-isoeyanate. decyl-isoeyanate, undecyî- isocyanate, dodeeyl-isocyanate, tridecyi-isocyanate, te tradecyl -isocyanate, cetyî- isocyanate, 2-eihyl-hexyl-isocyanate, n-octyl-isocyanate, isononyl-isocyanate, stearyl -isocyanate ;

• the cycïoalkyl-monoisocyanates compounds including cycîohexyl isocyanate, 1 -isocyanatomethyî- 1, 3,3-trimethyîcy ohexane.

Les composés monoisocyanates (Al) préférés sont 2-ethyi-hexanol-isocyanate, hexyî-isoeyanate, heptyl-isocyanate, octyl-isocyanate, n-nonyl-isocyanate, 2-ethyl-hexyl-isocyanate, n-octyl-isoeyanate, isononyl-isocyanate,

According to the invention, ie compound (A2) is derived from the pre-reaction and separated from at least one compound (A2 ~ i) and at least one compound (A2-2),

Advantageously according to the invention, the urethane compound according to the invention is prepared by the implementation of a molar amount of compound (A2- 1) which is greater than or equal to the molar amount of compound (A2-2) . Preferably, the molar amount of functional groups comprising at least one labile hydrogen, in particular the molar amount of hydroxyl groups of the compound (A2-1) is greater than or equal to the molar amount of isocyanate functions of compound (A2- 2).

Thus, the diisocyanate compound (A2-2) is totalemen transformed or completely consumed in the reaction for preparing the monoisocyanate compound (A2). It is not present and therefore not involved as such in the reaction which uses the compound (8) and (C).

Moreover and essential manner according to the invention, the asymmetrical nature of the diisocyanate compound (A2-2) leads to a different réaciivité of two isocyanate functions comprising, Indeed, in general, the reaction kinetics of the two functions isoeyanates are different. Thus, the urethane compound according to the invention is functionalized in a controlled manner.

As another nionoisocyanate compound, the condensation reaction according to the invention can also implement a nionoisocyanate compound (A2), According to the invention, the compound (A2) is prepared {uring a separate reaction of the condensation reaction according to the invention. The monoisocvanate compound (A2) is derived from the reaction:

® (a2-1) of at least one compound comprising at least one labile hydrogen atom and * (A2-2) of at least one asymmetric diisocyanate compound.

Preferably according to the invention, the compound of the preparation reaction (A2) is a catalyzed reaction.

More preferably according to the invention, the reaction is catalyzed by means of acetic acid, an amino, preferably l, 8-diazabieyelo [5.4.Q] undec -7-ene (DBU) or at least one derivative of a metal selected from Al, Bi, Sn, Hg, Pb, Mn, Zn, Zr, " fi. traces of water may also participate in the catalysis of the reaction.

Examples of metal compounds, preferred is a derivative selected from dibutyl bismuth diacetate, dibutyl bismuth oxide, dibutyl bismuth, bismuth carboxylate, dibutyl tin diacetate, dibutyl tin, dibutyltin oxide, a mercury derivative , a lead compound, zinc salts, manganese salts, a compound comprising zirconium Elate c, a compound comprising aluminum chelate. The preferred metal compound is selected from a derivative of Bi and a compound of Sn.

According to the invention, the nionoisocyanate compound (A2) is prepared by prior condensaiion of at least one compound (A2-1) and at least one compound (A2-2). Once the condensation reaction carried out, the nionoisocyanate compound (A2) has only one residual reactive isocyanate function.

The compound (A2-1) is preferably a compound comprising at least one labile and reactive hydrogen atom with the asymmetrical diisocyanate compound. More

/

preferably, it is a compound (a2-1) having at least one hydroxyl group. More preferably, the compound (A2-1) is a monoalcohol, eg monoalcoo! linear, branched or cyclic Cs-Cu, in particular a linear monohydric alcohol is branched C6-Ci4, in particular a monoalcoo! linear, branched or cyclic CS-CÏ.2.

Other compounds (A2-I) according to the invention can be used a compound comprising a primary amine or a secondary amine function; a carboxylic acid; a mercaptan compound.

The compound (A2-2) is preferred! eïlement one compound selected from aromatic diisocyanate compounds and alicyclic dissymmetric asymmetric diisocyanates compounds. As preferred examples of compounds (A2 ~ 2), can be used a compound selected from 2 > 4'-diîsoeyanate diphenylmethylene (2,4'-MDI), 2,4'-dibenzyl diisocyanate (2,4'-dBDI) , toluene 2,4-diisocyartate (2,4-TDI) and isophorone diisocyanate (IPDI).

In addition to the monoisocyanate compound (A), the condensation reaction also implements a compound (B) comprising more than two isocyanate functional groups. Preferably, compound (B) is an isocyanate compound comprising 3, 4, 5 or 6 isocyanate functional groups, more prefer! Ellem and it comprises three isocyanate functional groups,

According to the invention, the compound (B) may also be selected from isocyanate compounds comprising more than 2.5 isocyanate functions, preferably more than 2.6 isocyanate functional groups, more preferably more than 2.7 isocyanate functional groups, more preferably 3 or more than 3 isocyanate functions.

Examples of compounds (B) preferred according to the invention is used:

* le triphenyl.methane-4,4'}4"-triisocyanate ou le Ι, , '-methy!idynetris

(4-isocyanatobenzene) ; ou

* An isocyanurate compound, particularly an isocyanurate compound with a compound selected from:

o symmetrical aromatic diisocyanate compounds, preferably:

2.2 * î -diisGcyanate of diphénylméthyîène (2,2'-MDI) and 4,4-diisocyanate of diphénylméthyîène (4,4 '~ MDI);

« 4,4'-dibenzyî diisocyanate (4,4'~DBDÏ) ;

* 2,6-toluene diisocyanate (2,6-TDI);

* m~xylylène diisocyanate (m-XDI) ;

o alicyciiques symmetrical diisocyanate compounds, preferably methylene bis (4 ~ cyciohexylisocyanate) (H12MDI);

o aliphatiqu.es symmetrical diisocyanates compounds, preferably hexamethylene diisocyanate (HDI), pentamethylene diisocyanate

(Fdi);

o aromatic diisocyanate compounds asymmetrical, preferably:

* 2.4 of diphénylméihylène diisocyanate (2.4 ~ MDI);

* 2,4'-dibenzy! diisocyanate (2,4'-DBDÏ) ;

* 2,4-toluene diisocyanate (2,4-TDI):

a compound trimer biurea, especially a trimer compound of biurea a compound selected from:

symmetrical aromatic diisocyanate compounds, preferably:

8 2 5 2 1 ~ diisoeyanate of diphénylméthyîène (2,2'-MDI) and 4,4' diphénylméthyîène diisocyanate (4,4 ? -MDI);

* 4,4'~dihenzy! diisocyanate (4,4'-DBDI) ;

* 2,6-toluene diisocyanate (2,6-TDI);

* m-xylylène diisocyanate (m~XDl) ;

the alicyciiques symmetrical diisocyanate compounds, preferably methylene bis (4 ~ cycIohexylisocyanate) (H12MDI);

the compounds symmetrical aliphatic diisocyanates, preferably hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI);

aromatic diisocyanate compounds asymmetrical, preferably:

* 2.4 ~ diphénylméthyîène diisocyanate (MDI 2.4);

88 2s4'-dihenzyl diisocyanate (2,4'-DBDÎ) ;

" Toluene 2,4-diisocyanate (2,4-TDI);

"The alicyclic diisocyanate compounds asymmetrical, preferably isophorone diisocyanate (IPDI),

According to the invention, the compound (B) is preferably selected panni triphenylntethane-4,4 ' 5 4 "triisocyanate ~ > l 5 I
(4-isocyanatobenzene), an isocyanurate of HDI, an isocyanurate of IPDI, an isocyanurate of PDI . a biurea HDI trimer and IPDI trimer biurea, a biurea trimer PDI,

In addition to compounds (A) and (B), the condensation reaction also implements a compound (C) of formula (I).

Preferably, the compound (C) is a compound of formula (I) wherein:

* L represents independently a residue posy (ethylene glycol); or

® n represents a number from 50 to 400; or

"L independently represents a residue poly (ethylene glycol) and n represents a number from 50 to 400.

More preferably, the compound (C) is a compound of formula (I) wherein:

"L independently represents a poly residue (élhyiènegiycol); or

* N is a number ranging from 100 to 300; or

"I, is independently resid poly (éthySèneglycol) and n represents a number from 100 to 300,

Also preferably, the compound (C) is a compound having a molecular weight (Mw) is 1 500 to 20 000 g / mol, preferably from 2 000 to 20 000 g / mol, more preferably from 4 000 to 15 0GQ g / mol according to the invention, the molecular weight is calculated from the hydroxyl value determined by the DIN 53240-1 standard, now standard DIN EN ISO 4629-1, using the formula F: (56 100 x functionality Oïl groups) / hydroxyl number.

When the condensation reaction for preparing the urethane compound according to the invention, the amounts of compounds (A), (B) and (C) may vary. Preferably, the molar amount of compound (C) is about two times less than the molar amount of the monoisocyanate compound (A).

In addition to the urethane compound, the invention also relates to a process for preparing this compound. Thus, the invention provides a method for preparing an urethane compound in the absence of any compound diisocyanate by reacting:

(A) at least one monoisocyanate compound selected from:

(Al) a compound comprising a single isocyanate function and

(A2) at least one monoisocyanate compound from the separated reaction

(A2-1) of at least one compound comprising at least one labile hydrogen atom and

(A2-2) of at least one asymmetric diisocyanate compound,

(B) at least one isocyanate compound comprising more than two isocyanate functions, and

(C) at least one compound of formula (1):

(I)

wherein L represents independently a residue poly (alkylèneglycoî) and n represents a number from 40 to 400.

Preferably according to the invention for the method according to the invention, the condensation of the compounds (A), (B) and (C) is conducted in the presence of a catalyst. This catalyst may be selected from acetic acid, an amine, preferably l, 8-diazabieyclo [5.4,0] Undee ~ 7 ~ ene (DBU), a derivative of a metal selected from Al, Bi, Sn, Hg , Pb, Mn, Zn, Zr, Ti, preferably selected from dilauraîe dibutyl bismuth diacetate, dibutyl bismuth oxide, dibutyl bismuth, bismuth carboxylate, dilauraîe dibutyl tin diacetate, dibutyl tin dibutyl oxide of tin, a mercury derivative, a lead compound, zinc salts, manganese salts, a compound comprising zirconium chelate, a chelate compound comprising aluminum. The preferred metal compound is selected from a derivative of Bi and a compound of Sn.

For the process according to the invention, the monoisocyanate compounds (Al) and (A2) include only one isocyanate function. The reaction of these compounds with compounds (B) and (C) is therefore performed in the absence of diisocyanate compound.

Preferably for the method according to the invention, the monoisoeyanate compound (Al) is a compound of formula (II):

R-NCO

(II)

wherein R represents a linear, branched or cyclic, saturated, unsaturated or aromatic, preferably a linear alkyl group, branched or cyclic containing from 6 to 20 carbon atoms or a linear alkenyl, branched or cyclic containing from 6 to 20 carbon atoms,

Also preferably the method according to the invention, the nionoisocyanaie compound (Al) is a compound selected from:

« les composés monoisocyanates aromatiques, notamment phenyl isocyanate, diphenylmethane monoisoeyanate, 2-phenyiethyî isocyanate, 4-tolyl isocyanate, 2-tolyl isocyanate, 2,S~dimethylphenyl isocyanate, 3,4-dimethyiphenyl isocyanate,

2,3-dimethylphenyl isocyanate, 4-isocyanato~4'-methyldiphenylraethane ;

* Aromatic monoisocyanates multifunctional compounds, including 2 ~ methoxy ~ 4 ~ nitrophenyl isocyanate polymethylene polyphenyl! isocyanate

® les composés aîkyl-monoisocyanates, notamment hexyl-isocyanate, heptyl- isocyanate, octyl-isocyanate, n-nonyl-isocyanate, decyl-isocyanate, un decyl- isocyanate, dodecyl-isocyanate, tridecyl-isocyanate, tetradecyl-isocyanate, cetyl- isocyanate, 2-ethyl-hexyl-isocyanate, n-octyl-isocyanate, isononyl-isocyanate, stearyl-isocyanate ;

* The cycloaîkyî-monoisocyanaies compounds including eyelohexyl-isocyanate, 1 -isoeyanatomethyl- 1, 3, 3-trimethylcyelûhexane,

Les composés (Al) préférés sont 2-ethyl~hexanol~isoeyanate> hexyl-isoeyanate, heptyl-isoeyanate, octyl-isocyanate, n-nonyl-isocyanate, 2-ethyl-hexyl-isocyanate, n-octyl-isoeyanate, isononyl-isocyanate.

For the process according to the invention, the înonoisocyanate compound (A2) is prepared by separately and prior condensation of at least one compound (A2-1) and at least one compound (A2-2),

Advantageously for the process according to the invention, the compound (A2-1) is implemented in a molar amount which is greater than or equal to the molar amount of compound (A2-2). Preferably for the method according to the invention, the molar amount of functional groups comprising at least one labile hydrogen, in particular the molar amount of hydroxyl groups of compound (A2-I) is greater than or brightens the molar amount of isocyanate functions of compound (A2-2). Thus, the diisocyanate compound (A2-2) is fully converted during the reaction for preparing the compound (A2). It is not present, as the diisocyanate compound to the fact that its isocyanate functions is reacted with the compound (A2-I). It does therefore not involved in the reaction, which implements the compounds (B) and (C).

Moreover and essential manner to the method according to the invention, the asymmetrical nature of the diisocyanate compound (A2-2) leads to a different reactivity of the two isocyanate functions it comprises. Indeed, in general, the reaction kinetics of the two isocyanate functions are different. Thus, the method according to the invention allows to control the functionality of the prepared urethane compound.

As another înonoisocyanate compound, the method of the invention may also implement a monoisocyanaie compound (A2). For the process according to the invention, the compound (A2). prepared in a separate reaction of the condensation reaction according to the invention. The monoisocyanate compound (A2) is derived from the reaction:

(A2-1) of at least one compound comprising at least one labil hydrogen and

(A2-2) of at least one asymmetric diisocyanate compound.

Preferably for the method of invention, the reaction for preparing the monoisocyanate compound (A2) is a catalyzed reaction.

More preferably for the method according to the invention, the reaction is catalyzed by means of acetic acid, an amine, preferably by means of l, 8-diazabicydo [5.4.G] undec -7-ene (PB ! ) }, or at least a derivative of a metal selected from Al Bi, Sn, Hg, Pb, Mn, Zn, Zr, TL traces of water may also participate in the catalysis of the reaction.

Examples of metal compounds, preferred is a compound selected from dibutyltin dilaurate bismuth diacetate, dibutyl bismuth oxide, dibutyl bismuth, bismuth carboxylate, dibutyl tin diacetate, dibutyl tin oxide, dibutyl tin, a derivative mercury, a lead compound, zinc salts, manganese salts, a compound comprising zirconium chelate, a chelate compound comprising aluminum. The preferred metal compound is selected from a derivative of Bi and a compound of Sn.

Furnace the method of the invention, the monoisocyanate compound (A2) is prepared by first condensing at least one compound (A2-1) and at least one compound (A2-2).

The compound (A2-1) is preferably a compound comprising at least one labiîe and reactive hydrogen atom with the asymmetrical diisocyanate compound. More preferably, it is a compound (A2-1) having at least one hydroxyl group. Particularly preferably, compound (A2-I) is a monohydric alcohol, for example a linear monohydric alcohol, branched or cyclic C5-C14, in particular a linear monohydric alcohol, branched or cyclic Ce-Cu, in particular a linear monohydric alcohol, branched or cyclic Cs-Cn. Other compounds (A2-1) according to the invention can be used a compound comprising a primary amine or a secondary amino function; a carboxylic acid; a mercaptan compound.

The compound (A2-2) is preferably a compound selected from aromatic diisocyanate compounds and unsymmetrical compounds alicyclic diisocyanates asymmetrical. As preferred examples of compounds (A2-2) may be used a compound selected from 2,4'-diisocyanate diphényîméthylène (2,4'-MDI), 2,4'-dibenzyl diisocyanate (2,4 '~ dBDI) , toluene 2,4-diisocyanate (2,4-TDI) and isophorone diisocyanate (IPDI).

In addition to the monoisocyanate compound (A), the method according to the invention also uses a compound (B) comprising more than two isocyanate functional groups. Preferably for the method according to the invention, the compound (B) is an isocyanate compound comprising 3, 4, 5 or 6 isocyanate functions. More préférentiellemeni, it includes 3 isocyanate functions.

For the process according Γ invention, the compound (B) may also be selected from isocyanate compounds comprising more than 2.5 isocyanate functions, preferably more than 2.6 isocyanate functions, more préférentiellemeni more than 2.7 isocyanate functions, yet préférentiellemeni more 3 or more than 3 isocyanate functions. Examples of compounds (B) preferred according to the method of the invention, are used:

* le iriphenylm.ethane-4s4',4"~triisocyanate ou le l,r,l"~methylidy.netris (4-isocyanatobenzene) ; ou

* An isocyanurate compound, in particular a isoeyanurate compound of a compound selected from:

o symmetrical aromatic diisocyanate compounds, preferably:

* 2.2 ! diisocyanate diphenylmethylene (2,2 '~ MDI) and 4,4'-diphenylmethylene diisocyanate (4,4-MDI);

88 4,4'-dibenzyl diisocyanate (4,4'~DBD!) ;

* 2,6-toluene diisocyanate (2,6-TDI);

» m-xylylène diisocyanate (m-XDI) ;

o alicyeliques symmetrical diisocyanate compounds, preferably methylene bis (4-cyclohexyl isocyanate) (H12 DI);

o aliphaiiques compounds symmetrical diisocyanates, preferably hexamethylene diisocyanate (HDI);

o aromatic diisocyanate compounds asymmetrical, preferably:

* 2.4 ~ dnsocyanate diphenylmethylene (2.4 ~ MDI);

* 2,4'-dibenzyl diisocyanate (2,4'-DBDi) ;

* 2,4-toluene diisocyanate (2,4-TDI);

* A compound trimer biurea, especially a trimer biurea compound of ' a compound selected from;

o symmetrical aromatic diisocyanate compounds, preferably:

* 2,2'-diphenylmethylene diisocyanate (2,2'-MDI) and 4,4 - methylene diphenyl diisocyanate (4,4-MDI);

'* 4,4'-dibenzyl diisocyanate (4,4S~DBDI) ;

* 2,6-toluene diisocyanate (2,6-TDI);

s ra-xylylène diisocyanate (m-XDÎ) ;

o alicyclic diisocyanate compounds symmetrical, preferably methylene bis (4-cycîohexylisocyanate) (H12MDI);

o His diisocyanate compounds alip atic symmetrical, preferably hexamethylene diisocyanate (HDI);

o aromatic diisocyanate compounds asymmetrical, preferably;

* 2,4'-diphenylmethylene diisocyanate (2,4 f MDI};

* 2,4'-dibenzyl diisocyanate (2,4'-DBDI) ;

* 2,4-toluene diisocyanate (2,4-TDI);

* The alicyclic diisocyanate compounds asymmetrical, preferably isophorone diisocyanate (IPDI).

Pour le procédé selon l'invention, the composé (B) east préférentiellement Das Models triphenylmetibane-4,4 ', 4 "-triisocyanate, Ι, Γ, Ι" -melhylidynetris (4-isocyanatobenzene), an isocyanurate of HDI, an isocyanurate of IPDI, a trimeric de biurée of a trimeric HDI et de biurée of IPDI.

In addition to compounds (A) and (B), the method according to the invention also uses a compound (C) of formula (I). Preferably, the compound (C) is a compound of formula (I) wherein:

* L represents independently a residue poly (ethylene glycol); or

* N is a number from 50 to 400; or

* L represents independently a residue poly (ethylene glycol) and n represents a number from 50 to 400.

More preferably, the compound (C) is: a compound of formula (I) wherein:

® L independently represents a residue poly (ethylene glycol); or

® n represents a number from 100 to 300; or

* L represents independently a residue poly (éthyléneglyeol) and n represents a number from 100 to 300.

Also preferably for the method according to the invention, the compound (C) is a compound having a molecular weight (Mw) is from 1 500-20 000 g / I, preferably from 2 000 to 20 000 g / mol, most prefer! eilement 4 000 to 15 000 g / mol,

When the condensation reaction for preparing the urethane compound according to the invention, the amounts of compounds (A), (B) and (C) may vary. Preferably, the molar amount of compound (C) is about two times less than the molar amount of the monoisocyanate compound (A),

Further a urethane compound and a method, the invention also relates to an aqueous composition comprising at least one urethane compound according to the invention,

The invention also relates to an aqueous composition comprising at least one urethane compound prepared by the process of the invention.

The aqueous composition according to the invention may also comprise at least one additive, particularly an additive selected pamii:

"Amphiphiie a compound, in particular a surface-active compound, preferably a surfactant hydroxy compound, e.g. aJkyî-polyaîkyleneglycol include alkyl polyethylene glycol and alkyl polypropylene glycol;

• a derivative poîysaccharide, for example cyclodextrin, cyclodextrin derivative, polyethers;

® solvents including coalescing solvents and hydrotropic compounds, for example glycol, butylglycol, butyldiglycol, monopropylene ethyieneglycol, ethylenediglycol, Dowanol products (CAS number 34590-94-8), Texanol products (CAS number 25265-77-4);

® defoamers, biocides.

The invention also provides an aqueous formulation that can be used in many technical fields. The aqueous formulation according rinvenlion comprises at least one composition according V invention and may comprise at least one organic or inorganic pigment or organic particles, organometallic or inorganic, e.g., calcium carbonate, talc, kaolin, mica, silicates, silica, metal oxides, especially titanium dioxide, iron oxides,

The aqueous formulation according to the invention may also comprise at least one agent selected panni a particle spacer agent, a dispersing agent, a steric stabilizer, an electrostatic stabilizing agent, an opacifying agent, a solvent, a coaleseence agent, an agent antifoam, a preservative, a biocide agent, a spreading agent, a thickening agent, a filrnogène copolymer and mixtures thereof.

According to the particular urethane compound or additives comprising the formulation according to the invention can be implemented in many technical fields, Thus, the formulation according to the invention can be a coating formulation. Preferably, the formulation according to the invention is an ink formulation, an adhesive formulation, a lacquer formulation, a paint formulation, for example decorative paint or industrial coating. Preferably, the formulation according to the invention is a paint formulation.

The invention also provides a concentrated aqueous pigment paste comprising at least one urethane compound according to the invention and at least one organic or inorganic colored pigment

The urethane compound according to the invention has properties allowing its use to modify or control the rheology of the medium comprising the same. Thus, the invention also provides a method for controlling the viscosity of an aqueous composition.

This viscosity controlling method according to the invention comprises adding at least one urethane compound according to the invention in an aqueous composition. This process of

viscosity control may also comprise adding at least one urethane compound prepared by the process of the invention.

Preferably, the viscosity controlling method according to the invention is implemented by means of an aqueous composition according to the invention.

Also preferably, the viscosity controlling method according to the invention is implemented by means of an aqueous formulation according to the invention.

The following examples illustrate various aspects of the invention.

Example 1: Preparation of compounds urémanes .. ccording to the invention:

In a glass reactor of 3 L (the container 1) equipped with a mechanical stirrer, a vacuum pump, a nitrogen inlet and heated by a jacket in which oil circulates, are introduced 594.4 g of compound (C) (glycoî polyethylene molecular mass (Mw) of 10,000 or PEG 10,000), this medium is stirred. heated at I05 ° C and placed under inert atmosphere.

Meanwhile, in a three-necked glass flask of 100 mL (container 2) were introduced 39.59 g of compound (A2-2) (IPDI) to which is added 1.19 g of bismuth catalyst (bismuth carboxylate) . the medium was purged with nitrogen then heated to 50 ° C. When this temperature is reached, gradually introduced 23.18 g of compound (A2-1) (octan-l-ol) by means of a syringe.

After complete addition, the mixture repowered! is stirred for 15 minutes. Then, it is verified that the theoretical rate of NCO functions is achieved by a back titration. Is taken réaciionnel 1 g of the medium to which an excess of dibutylamine (1 molar, for example) which reacts with the isocyanate functional groups present in the medium. Dibutylamine unreacted is then assayed with hydrochloric acid (I for example). then it can be deduced the amount of isocyanate functional groups present in the reaction medium.

WE CLAIM

urethane compound prepared ers the absence of any diisoeyanale compound by reacting:

(A) at least one monoisocyanate compound selected from;

(Al) a compound comprising a single isocyanate functional group and (A2) at least one monoisocyanate compound from the separated reaction

(A2-1) of at least one compound comprising at least one labile hydrogen atom and

(A2-2) of at least one asymmetric diisocyanate compound,

(B) at least one isocyanate compound comprising more than two isocyanate functions, and

(C) at least one compound of formula (1):

0)

wherein L represents independently a residue of poly (alkylene glycol) and n represents a number from 40 to 400.

2. A compound as urethane according to claim 1 wherein the monoisocyanate compound (Al) is:

® a compound of formula (II):

R-NCG

(II)

wherein R represents a linear, branched or cyclic, saturated, unsaturated or aromatic, preferably a linear alkyl group, branched or cyclic containing from 6 to 20 carbon atoms or a linear alkenyl, branched or cyclic containing from 6 to 20 carbon atoms; Where is

• a compound selected from;

o les composés monoisocyanates aromatiques, notamment phenyl isocyanate, diphenylmethane monoisocyanate, 2~phenylethyl isocyanate, 4~toIyl isocyanate, 2-tolyl isocyanate, 2,5-dimethylphenyl isocyanate, 3,4-dimethylpheny! isocyanate, 2.3-dimethylphenyl isocyanate, 4-isocyanato-4'-methyldiphenylmethane ;

monoisocyanates polyfunctional aromatic compounds s, in particular 2 ~ I ~ 4 ~ † .hoxy nitropheriyi isocyanate, poly methylene polyphenyl isocyanate;

les composés aîkyl-monoisocyanates, notamment hexyl-isoeyanate, heptyî-isocyanate, octyî-isocyanate, n-nonyl-isocyanate, decyl-isocyanate, undecyl-isocyanate, dodecyl -isocyanate, tridecyl-isocyanate, tetradecyl- isocyanate, cetyl-isocyanate, 2-ethyl-hexyI~isocyanate, n-octyl-isocyanate, isononyl-isocyanate, stearyl-isocyanate ;

the cycloalkyl monoisocyanates compounds, including cyclohexyl isocyanate, T ~ isocyanatomethyl-3 " 3-trimethylcyclohexane.

3. A compound as urethane according to one of claims 1 and. 2 wherein the reaction for preparing the monoisoeyanate compound (A2) is a catalysed reaction, preferably catalyzed by means of acetic acid, an amine, preferably l, 8-diazabicyclo [5.4.0] undec ~ 7- ene (DBU), or at least a derivative of a metal selected from al, Bi, Sn, Hg, Pb, Mn, Zn, Zr, Ti, for example dibutyl bismuth diacetate, dibutyl bismuth oxide, dibutyl bismuth, bismuth carboxylate, dibutyl tin diacetate, dibutyl tin dibutyl oxide of tin, a mercury derivative, a lead compound, zinc salts, manganese salts, a compound comprising zirconium chelate, a compound comprising Γ aluminum chelate,

4. A compound as urethane according to one of claims 1 to 3 wherein the compound (A2-1) is selected from a compound comprising at least one labile and reactive hydrogen atom with the asymmetrical diisocyanate compound; a compound comprising at least one hydroxyfe group; a compound comprising a primary amine or a secondary amine function; a carboxylic acid; a mercapto compound; preferably a compound comprising a hydroxyl group. notammeni a monohydric alcohol, for example a monoalcohol linear, branched or cyclic Cs-Cu, in particular a linear monohydric alcohol, branched or cyclic CS-CM, including a linear monohydric alcohol, branched or cyclic Cg ~ Ci2.

5. A compound urethane according to one of claims 1 to 4 wherein the compound (A2-2) is selected from:

® dissymmetric aromatic diisocyanate compounds, preferably 2,4'-diphenylmethylene diisocyanate (2,4 - di), 2,4'-dibenzyl diisocyanate (2,4'- dBDI), toluene 2,4-diisocyaixate (2 , 4-TDI);

® cyclic diisocyanates ali unsymmetrical compounds, preferably isophorone diisocyanate (IPDI).

6. A compound urethane according to one of claims 1 to 5 wherein;

• the compound (B) is an isocyanate compound comprising 3, 4, 5 or 6 isocyanate functions; or for which

· The compound (B) is an isocyanate compound comprising more than 2.5 isocyanate functions, preferably more than 2.6 isocyanate functional groups, more preferably more than 2.7 isocyanate functional groups, more preferably 3 or more than three isocyanate functional groups; or for which

® compound (B) is triphenylnietharje-4,4 ', 4 "-triisocyanate or

î "-methylidynetris (4-isocyanatobenzene); or wherein

• the compound (B) is an isocyanurate compound, particularly an isocyanurate compound with a compound selected from;

o symmetrical aromatic diisocyanate compounds, preferably:

* 2.2 diphenylmethylene diisocyanate of {2,2'-MDI) and

4.4 ~ diphenylmethylene diisocyanate (4,4-MDI);

* 4,4'~dibenzyl diisocyanate (4,4*-DBDI) ;

s 2.6-isocyanate of toluene (2,6-TDI);

* m-xylylène diisocyanate (m-XDI) ;

o alicyclic diisocyanate compounds symmetrical, preferably methylene bis (4-cyclohexy1isocyanate) (HÎÎMDI);

o symmetric aliphatic diisocyanate compounds, preferably hexaméihyiène diisocyanate (HDI), pentamethylene diisocyanate (PDI);

o aromatic diisocyanate compounds asymmetrical, preferably;

■ * 2,4'-diphenylmethylene diisocyanate (2,4'-MDI);

* 2,4'-dibenzyl diisocyanate (2,4'~DBDI) ;

s 2,4-toluene diisocyanate of (2,4-TDI);

® compound (B) is a trimer biurea compound, a compound noiammeni biurea trimer of a compound selected from:

o symmetrical diisocyanat.es aromatic compounds, preferably:

And 2,2'-diisocyanate of diphénylrnéthylène (2,2'-MDI) and 4,4'-diisocyanate diphénylméthylène of (4 S 4'-MDI);

* 4,4'-dihenzyl diisocyanate (4,4'-DBDI) ;

■ * 2,6-toluene diisocyanate (2,6-TDI);

* m-xylylène diisocyanate (rn-XDI) ;

o alicyclic diisocyanate compounds symmetrical, preferably methylene bis (4-cyclohexyl isocyanate) (H 12 MDI);

o symmetric aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDJ), pentamethylene diisocyanate

(PDI);

o aromatic diisocyanate compounds asymmetrical, preferably:

* 2,4'-diphenylmethylene diisocyanate (2,4-MDI);

* 2,4'~dibenzyl diisocyanate (2,4'-DBDI) ;

* 2,4-toluene diisoeyanate (2,4-TDI);

* The alicyclic diisocyanate compounds asymmetrical, preferably isophorone diisocyanate (IPDT).

1. A compound urethane according to one of claims 1 to 6 wherein the compound (C) is a compound of formula (I) wherein:

"L independently represents a residue poly (ethylene glycol); or

® n represents a number from 50 to 400, preferably 100 to 300; or "L independently represents a poly residue (éthylèneglycoî) and n represents a number from 50 to 400, preferably from 100 to 300,

8. A compound urethane according to one of claims 1 to 7 wherein the compound of formula (Γ) has a molecular weight (Mw) of from 1 500 to 20 000 g / mol, preferably from 2 000 to 20 000 g / mol, more preferably from 4 000 to 15 000 g / mol,

9. A compound urethane according to one of Claims 1 to 8 for which the molar amount of compound (C) is about two times less than the molar amount of monoisoeyanate compound (A),

10. A method for preparing an urethane compound in the absence of any compound di isocyanate, by reaction:

(A) at least one monoisocyanate compound selected from:

(In) a compound comprising a single isocyanate function and

(A2) at least one monoisocyanate compound from the separated reaction

(A2-1) of at least one compound comprising at least one labile hydrogen atom and

(A2-2) of at least one asymmetric diisocyanate compound,

(B) at least one isocyanate compound comprising more than two isocyanate functions, and

(C) at least one compound of formula (i):

(HO) - - (OH)

(I)

wherein L represents independently a residue poly (alkylèneglyeol) and n represents a number from 40 to 400.

1 1. The method of claim 10 for the preparation of a urethane compound according to one of claims 1 to 9.

12. An aqueous composition comprising:

® at least one compound selected from a urethane compound according to one of Claims 1 to 9 and a urethane compound prepared by the process of claims 10 or 11, and optionally

* At least one additive chosen from:

o an amphiphilic compound, in particular a surface-active compound, preferably a surfactant dihydroxy compound, for example alkyl polyalkylene glycol include polyethylene glycol and alkyl polypropylene glycol alkyi-;

o of a polysaccharide derivative, for example cyclodextrin, cyclodextrin derivative, polyethers;

o solvents including coalescing solvents, and hydrotropes, e.g. glycoî, butylglycol, butyldiglycol, monopropylene glycol, ethylene glycol, ethylenediglycol, Dowanol products (CAS number 34590- 94-8), Texanol products (CAS number 25265-77-4);

o defoamers, biocides.

13. An aqueous formulation comprising;

• at least one composition according to claim 12; eventually

• au moins organique a pigment or mineral ou des Organiques fines, mineral or organo métalliques, par exemple of calcium carbonate, talc, kaolin, mica, silicates, silica, oxydes métalliques, notamment of oxyde de titane, oxydes de fer; et éventuellement

• at least one agent selected from a spacer agent particles, a dispersing agent, a steric stabilizer, an electrostatic stabilizing agent, an opacifying agent, a solvent, a coaîescence agent, an antifoaming agent, a preservative, an agent biocide, a spreading agent, a thickening agent, a film-forming copolymer and mixtures thereof.

14. Formulation of claim 13 coating, especially an ink formulation, a lacquer formulation, an adhesive formulation, a paint formulation, for example decorative paint or industrial coating.

15. Concentrated aqueous pigment paste comprising at least one urethane compound according to one of claims î to 9 or at least one urethane compound prepared by the process of claims 10 or 11 and at least one organic or inorganic colored pigment.

16. A method of controlling the viscosity of an aqueous composition comprising adding at least one urethane compound according to one of claims 1 to 9 or at least one urethane compound prepared by the process of claims 10 or i .

17. The method of claim 16 wherein the aqueous composition is a composition according to claim 12 or a formulation defined as claimed in one of claims 13 and 14,