EP2104706A1

EP2104706A1 - Pre-activated slurry as rheology additive

Info

Publication number: EP2104706A1
Application number: EP07856689A
Authority: EP
Inventors: Sébastien Caron; Elizabeth Pires; Susan Rimmer; Joël Roussel; Yohann Trang
Original assignee: Cray Valley SA
Current assignee: Arkema France SA
Priority date: 2006-12-21
Filing date: 2007-12-13
Publication date: 2009-09-30
Also published as: MX2009006427A; US20080153924A1; CN101568581B; KR20090103884A; EP1935934B1; CN101568581A; CA2671612A1; TWI444420B; CA2671612C; JP2008174743A; TW200838907A; KR101546312B1; JP5376799B2; EP1935934A1; WO2008080536A1; US7858074B2; ES2391779T3; PL1935934T3

Abstract

A pre-activated slurry as rhelogy additive having: A) at least one fatty acid diamide, provided as a powder, said powder having optionally, in addition to the diamide, hydrogenated castor oil, B) at least one organic plasticizer, said plasticizer being a liquid at room temperature. The invention also relates to a specific preparation method of the rheology additive, a composition comprising said additive, a method for preparing said composition, and specific uses and particularly specific coatings obtained from said additive.

Description

RHEOLOGY ADDITIVE AS PRE-ACTIVE PASTE

The present invention relates to rheology additives in the form of pre-activated paste, a specific method for preparing these additives, specific compositions comprising said additive, as well as a specific process for the preparation of said compositions, specific uses and specific coatings. obtained from said additives. These specific additives make it possible to modify the viscosity of compositions of mastics, glues, adhesives, coatings, such as paints, varnishes, gel coats, inks, or molding compositions. State-of-the-art compositions of polyurethane-based sealants, adhesives or coatings comprising a non-reactive polyamide additive are known to adjust the viscosity of said compositions. Indeed, EP 467 533 describes a polyamide obtained from at least one polycarboxylic acid chosen from sebacic acid, azelaic acid, dodecane dioic acid and dimers or trimers of fatty acids, with at least one compound comprising a group -NH2 or -NH selected from primary and secondary monoamines, natural and synthetic, saturated or unsaturated, either ethylenically unsaturated or acetylenically unsaturated. The polyamide rheology additive obtained can be prepared from a powder, or in combination with a solvent or a plasticizer, to form a liquid or a paste, said polyamide to be previously diluted.

JP 2004107543 discloses a thixotropic additive in the form of a grain-free paste, said paste being a reaction product between a diamide component and an epoxy resin added at the end of synthesis, said diamide component being chemically modified so as to react on the epoxy resin.

On the other hand, JP 2002146336 describes the preparation of a rheology additive in the form of a paste obtained by mixing fatty acid diamides, dispersed in an alcohol-based solvent, a cycloaliphatic compound and a an ester. The dispersion thus obtained is then subjected to a heat treatment. The final paste does not contain a plasticizer; it is then used as a thixotropic agent in unsaturated polyester resins.

JP 63-15876 discloses a mixture of hydrogenated castor oil and C14-C18 saturated fatty acid fatty acids with ethylene diamine or 1,4-diaminobutane, the thixotropic agent-forming mixture being usable. in single-component compositions of polyurethane mastic. However, said Thixotropic agent is not in the form of a pre-activated paste that can be used without prior activation.

Other rheology additives can be used to increase the viscosity of mastic or adhesive systems in solvent or solvent phase. Among these, mention may be made of polyamide powders, powders of derivatives based on hydrogenated castor oil, pyrogenic silicas, and precipitated or ground calcium carbonates. Pyrogenic silicas and calcium carbonates are of a mineral nature and require dispersion of the mixture at a very high speed. However, these mineral fillers have problems of stability and sedimentation over time, with negative effects on the mechanical properties of the final system. Another particular disadvantage of polyamide powders and hydrogenated castor oil derivatives is the need for activation of the system in the manufacture of the final application composition for the user (formulator). This activation requires high speed shearing and heating corresponding to temperature rises of up to about 120 ^° C. depending on the products, as well as a minimum necessary duration, depending on the temperature and system conditions (polarity), to develop optimal final rheological properties. These additives give the composition to which they are incorporated a thixotropic behavior characterized by a marked rheofluidification, that is to say a reduction in viscosity when the shear increases, then a recovery in viscosity dependent on time (equivalent to an effect hysteresis). This type of additive provides the final composition with excellent application properties which are characterized by a high resting viscosity, good stability of this storage viscosity, good anti-settling, ease of application and extrusion and good resistance to sag when applied. Despite the fact that this type of additive provides good properties to the final composition, it has as its main disadvantage the fact of needing an activation phase, sometimes difficult to control, difficult to reproduce by the end user, and expensive in time and energy.

The technical problem of the invention, compared to the state of the prior art cited, is therefore the development of an improved product having properties comparable to those provided by the polyamide powders and the derivatives of the invention. hydrogenated castor oil, without requiring an activation phase by the end user, said product being therefore easier and faster to implement by the end user, along with other special benefits related to the resolution of this general problem. The term "pre-activated paste" shall be understood to mean that the additive is ready for use by the end-user (formulator of sealants, glues, adhesives, or coatings such as paints, or varnish, or gel coats, or inks or molding composition), by simple mixing in the final application formulation, without the need for any specific in situ activation in this formulation (specific conditions of temperature, shear and duration to be respected). More particularly, these advantages related to the resolution of the general technical problem with respect to the state of the art are the following: low emissions of volatile organic compounds (VOCs) and less risk of ignition or explosion, absence of powders powdery to handle by the end user, which avoids the formation of dust in the atmosphere and the place of manufacture of the final compositions, and therefore the need for ventilation, to prevent breathing of this dust, possibility of handling in the absence of any solvent in the final formula, the additive can be used both in solvent application compositions that in solvent-free compositions, flexibility of use and handling, the pre-activated paste being easy to disperse within the composition, at the same time as the charges at the beginning of manufacture, or at the end of manufacture, while retaining properties rheological at least comparable to those obtained from powders of polyamide type, diamides or castor oil according to the state of the prior art, and last but not least, no need for the activation step, the implementation of the additive according to the invention does not require heating, high shear or activation time, which allows a gain:

"in production time, since there is no heating step, and that the cooling step is reduced or even eliminated, during the preparation of the final composition," in energy, due to the no heating and cooling,

• in productivity for the end user,

• Reproducibility and reliability of the final performances. Thus, the first subject of the invention is a rheology additive in the form of a pre-activated paste comprising:

A) at least one fatty acid diamide, introduced in powder form, said powder optionally being able to contain, in addition to said diamide, hydrogenated castor oil,

B) at least one organic plasticizer, said plasticizer being liquid at ambient temperature.

The second subject of the invention is a process for preparing such rheology additives by dispersion and activation by controlled heating. The invention also covers an organic binder composition or pigment concentrate or fillers comprising a rheology additive according to the present invention, as well as the process for preparing such a composition.

Another subject of the invention is the use of the rheology additive or the composition according to the invention for coating applications of paints, varnishes, inks, gel coats, PVC-based plastisols or for applications. mastics, glues, adhesives, sealants, molding compositions, or for cosmetic applications.

Finally, a final subject of the invention relates to finished articles such as coatings, seals, composites or molded parts, or cosmetics obtained from such an additive or such a composition according to the invention.

The first subject of the invention is therefore a rheology additive in the form of a pre-activated paste comprising:

Said rheology additive in pre-activated paste form preferably has an elastic dynamic modulus G ', measured on said mixture A) + B), at a temperature of 23 ° C. and at a frequency of 1 Hz, greater than or equal to 10 ⁴ Pa, preferably greater than or equal to 8.10 ⁴ Pa, and even more preferably greater than or equal to 5.10 ⁵ Pa. This characteristic is significant for the activation of the pre-activated additive. Preferably, said plasticizer is a polar organic plasticizer comprising at least one polar group, preferably an ether group and / or an ester group and / or an epoxy group.

Said plasticizer may initially comprise at least one ether group, and in this case it may be chosen from polyethers such as homopolymers and / or copolymers of ethylene oxide and / or propylene oxide and / or a mixture said polyethers (homopolymers and / or copolymers) and / or their derivatives, these derivatives comprising, inter alia, said polyethers blocked at the end of the chain by a C ₁ (methoxy) to C ₄ (butoxy) alkoxy group, or by a C2 ester group; C4 (butyrate) acetate, said polyethers having a weight average molecular weight Mw ranging from 150 to 6000, and preferably from

1000 to 3000. The term "copolymer" is to be understood as including both random and block copolymers.

Said plasticizer may then comprise at least one ester group, and it may be chosen from monoesters and / or polyesters (multifunctional esters), obtained from C 4 to C 21 alcohols, optionally alkoxylated alcohols, for example with 1 to 10 units. alkoxy chosen from oxyethylene (OE) and / or oxypropylene (OP) units, and from mono- or polyacids of functionality ranging from 1 to 4, selected from: - organic acids chosen from aromatic acids having a chain length (without -CO2H function) from Ce -C ₁ O and / or aliphatic acids having a chain length (without considering the functions -CO2H) ranging from C4 to C ₁ S, or mineral acids. The aromatic acid esters may be chosen from phthalates, trimellitic or trimellitates (benzene 1, 2,4-tricarboxylates) esters and their trimesitate isomers or trimesates (benzene 1,3,5-tricarboxylates). The aliphatic acid esters may be chosen from adipic (adipates), citric (citrates), sebacic (sebacates) and azelaic (azelates) esters. The esters of mineral acids may be chosen from sulphonic esters (sulphonates), in particular alkyl sulphonates of C ₁ -C 21, sulfuric (sulphates), sulfinic (sulfinates), phosphoric (phosphates), phosphonic (phosphonates) and phosphinic (phosphinates). Finally, said plasticizer may also comprise at least one epoxy group, and may be chosen from epoxidized oils based on fatty acids, whose chain length may range from C ₁₀ to C ₁₅ , such as epoxidized soy.

Preferably, in said rheology additive there is no other compound selected from alcohols of molecular weight Mw <150, such as methanol, ethanol, propanol, butanol or benzyl alcohol, or selected polar aprotic solvents such as N-methylpyrrolidone, N-ethylpyrrolidone, N-butylpyrrolidone, acetonitrile,

N, N-dimethylformamide, N, N'-dimethylacetamide, dimethylsulfoxide, N, N, N ', N'-tetramethylurea, hexamethylphosphoramide, hexamethylphosphorous triamide or propylene carbonate.

Among the preferred plasticizers, mention may be made of those comprising at least one aromatic acid ester group C ₈ -C ₁₀ , in particular the plasticizers selected from mono- and / or di-alkyl phthalates, and even more preferentially from the di- -alkylphthalates, with said alkyls being identical or different, and selected from C ₇ to C ₁ S alkyl, and preferably C ₁ O to Cu.

In this family of plasticizers (di-alkyl phthalates), the most preferred is di-iso-undecyl phthalate. In the family of polyethers, the most preferred are polyether homopolymers of propylene oxide (polypropylene glycols) with a weight average molecular weight Mw ranging from 1000 to 3000, and more particularly polypropylene glycol (PPG) of Mw equal to 2000, and / or their derivatives, chosen from monoesters, preferably C ₂ to C ₄ ) or C 1 to C ₄ monoethers, such as monomethoxylated or monoethoxylated derivatives. Said plasticizer may have a boiling point higher than

200 ° C, and preferably greater than 250 ⁰ C (at atmospheric pressure). It must be liquid at room temperature so that said diamide is dispersible in said plasticizer.

The rheology additive according to the invention preferably has a consistency or maximum penetration value, measured according to ASTM D 217, less than 15 mm, more preferably less than 10 mm, and even more preferably less than 5 mm.

Said fatty acid diamide introduced in powder form has a particle size of less than 100 μm, and preferably less than 50 μm, and more preferably at least 90% of said diamide has a particle size less than 20 microns, and preferably less than 15 microns.

The weight ratio of the fatty acid diamide can vary from 10 to 40%, and preferably from 15 to 30% relative to the mixture A) + B). A fatty acid diamide suitable for the invention may be obtained by polycondensation between at least one primary C2-C12 diamine and at least one C3-C22 chain-length monocarboxylic acid, the reaction product optionally being diluted in hydrogenated castor oil, and in this case at a level ranging from 10 to 100% by weight relative to the total diamide + hydrogenated castor oil, and preferably at a level ranging from 20 to 100% by weight . Hydrogenated castor oil can be used to adjust the affinity of the final mixture (diamide + hydrogenated castor oil) relative to the composition of the final formulation in application.

In the case where the diamide is diluted in hydrogenated castor oil, the addition is carried out at a temperature between 140 and 220 ^° C. At the end of the addition, a solid mass is obtained which is ground.

According to a preferred embodiment of the invention, the rheology additive according to the invention can be obtained by a specific method, as described below. The specific process for the preparation of said rheology additive, which is the second subject of the invention, comprises the following steps: i) gradual dispersion of said diamide in the form of a powder, in the plasticizer until a homogeneous dispersion is obtained, controlled temperature, through a temperature control, the diamide and said plasticizer being as defined above, ii) maintaining the homogeneous dispersion obtained in step i) in at least one isotherm with a corresponding temperature of 50 at 120 ⁰ C, and preferably ranging from 60 to 100 ⁰ C, for a period of 1 to 100 hours, preferably from 6 to 80 hours, and even more preferably from 15 to 40 hours.

The choice of the temperature and duration of step ii) is a function of the polarity of the plasticizer and its chemical affinity with said fatty acid diamide.

The homogeneity of the dispersion is characterized by an absence of grains, during the application of the film of said dispersion between two glass plates (test glass plates). To obtain this homogeneity, said diamide is dispersed in said plasticizer at a shear rate of preferably between 2 and 6 m. s ¹ , for laboratory scale preparation on a capacity not exceeding 1 liter. The end of step ii), also called "activation or maturation step", is characterized by a consistency or maximum penetration value of the formed paste of less than 15 mm, preferably less than 10 mm, and even more preferably, less than 5 mm, measured according to the ASTM D 217 standard. This maximum penetration value is to be associated with a reference method for the preparation of said pre-activated paste, which corresponds to a preparation at laboratory scale on a capacity not exceeding 1 liter, the sample thus being perfectly homogeneous. The method for preparing said preactivated paste is described below in the examples according to the invention.

The third subject of the invention relates to an organic binder composition or to a pigment concentrate or to fillers comprising at least one rheology additive as defined according to the invention or obtained according to the process as defined according to the invention, said composition being capable of be a coating composition, the latter can be used as a protective coating and / or decoration and / or surface treatment of various substrates, coating selected from paints, varnishes, gel coats pigmented or non-pigmented, inks, plastisols to PVC base, or a composition of putty, glue, adhesive, sealant, or molding composition for composites or molded parts, SMC or BMC type or laminated, types hulls of boats or panels composites, or castings, with application of the composition by spraying or brushing or rolling, or finally a composition of cosmetics.

Said rheology additive according to the invention, as described above, may be present in said composition, has a content in weight ranging from 1 to 40%, preferably from 15 to 30%, and even more preferably from 10 to 20% relative to the total weight of said composition, and said diamide may be present as a dry active ingredient at a content in weight ranging from 0.1 to 16%, preferably from 0.2 to 8%, and even more preferably from 1 to 6% relative to the total weight of said composition. The composition according to the invention may comprise other components such as, for example, fillers, plasticizers, wetting agents or pigments.

According to a more particular embodiment, the organic binder composition according to the invention is crosslinkable, either thermally or by irradiation under radiation such as VF (in the presence of at least one photoinitiator) and / or EB (beam of electrons, without initiator), including self-crosslinkable at room temperature, or it is non-crosslinkable. The organic binder composition may be crosslinkable single-component (a single reactive component) or bicomponent (binder based on two components reactive with each other by mixing during use).

Said organic binder can be selected from at least one epoxy-amine reactive system (crosslinkable bi-component), an unsaturated polyester, a vinylester, an epoxidized resin, a reactive silicone resin, a polyester-grafted alkyd or a polyamide or modified diurea -diurethane, or an ungrafted alkyd, a polyurethane or a silicone, a crosslinkable bi-component polyurethane, a polysiloxane, a polysulfide polymer, a reactive acrylic polymer, a multifunctional oligomer (meth) acrylate or acrylated acrylic oligomer or multifunctional allyl oligomer, an SBR-type elastomer, polychloroprene or butyl rubber, or a silane prepolymer, preferably a silane polyether or a silane polyurethane, or a silane polyether urethane with -OH or -CO2H function.

In a more particular case, said organic binder may be selected from the following cross-linkable two-component reactive systems: epoxy-amine or epoxy-polyamide systems comprising at least one epoxy resin comprising at least two epoxy groups and at least one amine compound or polyamide comprising at least two amino groups, the polyurethane systems comprising at least one polyisocyanate and at least one polyol, the polyol-melamine systems, and the polyester systems based on at least one epoxy or a reactive polyol with at least one corresponding acid or anhydride.

According to other particular cases, said organic binder can be a two-component crosslinkable polyurethane system or a polyester crosslinkable two-component system from an epoxy-acid or carboxylic anhydride reaction system, or a polyol-acid system. or carboxylic anhydride, or polyol-melamine reaction system wherein the polyol is a hydroxylated acrylic resin, or a polyester or polyether polyol.

According to one variant, the organic binder composition according to the invention is a sealant, adhesive, adhesive or sealant composition, which is self-crosslinkable, and based on polyether-silane or polyurethane- silane.

More particularly, the organic binder composition according to the invention may be a silylated (or silane-based, silylated pre-polymer mono- component sealant composition, which term is to be considered synonymous with silyl for the present invention), and preferably silylated polyether or silylated polyurethane (silylated polyether urethane), such as KANEKA MS POLYMER ™ and KANEKA SILYL ™. Polymeric MS can be used in: construction and building for expansion joints, glazing assembly, joinery joints, masonry joints, prefabricated (sandwich panels or refrigerated truck, for example), joints for parquet, industry for marine, automobile (industrial bodywork, windshield seals), large distribution for sealants and adhesives, with and without solvent, civil engineering. Other components may be added or substituted for silylated pre-polymer single-component sealant compositions, such as other types of binders, colored pigments, various plasticizers, precipitated or ground calcium carbonate fillers, glyceride derivatives, silicas, such as pyrogenic silicas, other additives such as UVA (UV antioxidants), such as 2,4-diterbutyl-6- (5-chlorobenzotriazol-2-yl) phenol (Tinuvin) ^® 327 from Ciba), light stabilizers based on sterically hindered amines, such as HALS (Hindered Amine Light Stabilizers), such as bis (2, 2,6,6-tetramethyl-4-piperidyl) sebacate (Tinuvin ^® 770 of Ciba), waxes, and other types of catalysts, such as tin salts. The invention also comprises a process for preparing said composition according to the invention, said process comprising the following steps: i) adding said additive according to the invention to said composition, ii) homogenization of the mixture with a kneader and / or planetary mixer and / or high speed disperser, without having any need, at this stage, to apply an activation treatment. Said process for preparing said organic binder composition according to the invention may also comprise a preliminary step of preparation of said additive, according to the following process: i) preparation of an additive according to the invention, according to the process for the preparation of said additive of the invention, as defined above, ii) adding said additive obtained according to step i) in said composition, as defined above, iii) homogenization of the mixture in a kneader and / or planetary mixer and / or high speed disperser , without having any need, at this stage, to apply an activation treatment. The term "high speed" means tangential speeds ranging from 2 to 15 m. s ¹ .

Another object according to the invention relates to the use of at least one rheology additive or a composition according to the present invention, without the need for activation in situ, by simple addition and homogenization in the final formula. More particularly, said rheology additive and said composition may be used in coating applications, such as coatings for paints, varnishes, inks, pigmented or unpigmented gels coats, or PVC-based plastisols, or in sealants, glues, adhesives, sealants, composites, moldings, SMC / BMC laminates, or in cosmetic applications such as nail polish.

Finally, the final subject of the invention concerns finished objects such as coatings obtained from the use of at least one rheology additive or composition according to the present invention, or by the use of the methods of respective coatings, said coatings being selected from pigmented or non-pigmented paints, varnishes, inks, or gel coats, or PVC-based plastisols, or caulks, or adhesives, or adhesives, or seals, or composites, or molded parts, or SMC / BMC laminates resulting from molding compositions, or cosmetics, such as nail polish As an illustration of the invention, the following examples demonstrate without any limitation, the performance of the rheology additive according to the present invention.

I- Raw materials used

Table 1

II - Preparation and characterization of rheology additives: fatty acid diamide and pre-activated paste

Preparation of the fatty acid diamide

450 g of 12-hydroxystearic acid and 430 g of capric acid are heated at 80 ^° C. 120 g of ethylenediamine are then charged. The amine reacts immediately with the acids to form the corresponding salts. This results in an exothermic reaction which increases the temperature in the reactor from 80 to 130 ^° C. The reactor is then heated rapidly until the temperature of the batch reaches 200 ° C. The reactor is then maintained at this temperature until the acid and amine values are below 6 mg KOH / g. The contents of the reactor are then discharged, cooled and finely ground.

Pasta preparation:

Reference examples (non-pre-activated compositions):

a) Plasticizer: DIUP

100 g of previously ground fatty acid diamide and 300 g of di-iso-undecyl phthalate (DIUP) are dispersed for 1 hour using a disperser

Dispermat ^® CV with a 4 cm diameter, at a speed of

2000 rpm, or rpm, at a temperature not exceeding 20 ^° C., by regulating the temperature by circulation of cold water.

b) Plasticizer: PPG 2000

100 g of grinded fatty acid diamide and 300 g of polypropylene glycol mass 2000 (PPG 2000) are dispersed for 1 hour using a Dispermat ^® CV disperser equipped with a pale 4 cm in diameter, at a speed of 2000 rpm, or rpm, at a temperature not exceeding 20 ^° C., by regulating the temperature by circulation of cold water.

Examples of the invention (pre-activated pastes):

a) Plasticizer: DIUP The same procedure as for the reference example is followed, with an additional stage of maturation, of introducing the non-pre-activated composition into an oven preheated to 80 ^° C. for 24 hours.

b) Plasticizer: PPG 2000

The same procedure as for the reference example is followed, with an additional stage of maturation, of introducing the non-pre-activated composition into an oven preheated to 80 ^° C. for 24 hours. Rheological characterization of pasta:

The rheology of the pastes is monitored at 23 ° ^C. using an imposed stress rheometer MCR301 (Anton Paar), with a sandblasted plane-plane geometry 25 mm in diameter, and with a gap of 0.5 mm.

1) Activation tracking

The activation of the pastes was evaluated by dynamically monitoring the elastic modulus (C) and the viscous modulus (G ") of the pastes, as a function of the maturation time.The modules were measured on samples at different times. maturation (measurements were made 10 minutes after leaving the oven, the time that the temperature of the sample drops to 23 ⁰ C).

The stress τ is chosen so as to be in the linear zone (at low deformations). The frequency used is 1 Hz.

The corresponding curves are presented in Figures 1 and 2.

2) Frequency mechanical spectra

The mechanical frequency spectra of the pastes were made at 23 ° C.

The evolution of the elastic (G) and viscous (G ") modules, as a function of frequency, was followed in dynamic mode.

The corresponding curves are presented in Figures 3 and 4.

III - Preparation and use of rheology additives for the preparation of sealants

Preparation of pre-activated pasta:

a) Plasticizer: DIUP

250 g of the previously milled fatty acid diamide and 750 g of di-iso-undecyl phthalate (DIUP) are loaded into a 1-liter can (height: 13 cm, diameter: 11 cm), at room temperature. Using a Dispermat ^® CV disperser with a 4 cm diameter paddle, the two products are mixed at 1500 rpm for 15 min at a temperature of not exceeding 20 ^° C., by regulating the temperature by circulation of cold water. The box is then closed carefully and introduced into an oven preheated to 70 ° C for 24 hours.

The final product is a soft, white paste, characterized by a dry active ingredient content of 25%, and a penetration resistance measured according to ASTM D 217 standard of 2.00 mm.

b) Plasticizer: PPG 2000

250 g of the fatty acid diamide previously ground and 750 g of polypropylene glycol mass 2000 (PPG 2000) are loaded into a 1 liter canister (height: 13 cm, diameter: 1 1 cm), at room temperature. Using a Dispermat® CV disperser equipped with a 4 cm diameter paddle, the two products are mixed at 1500 rpm for 15 min, at a temperature not exceeding 20 ^° C., by circulating temperature regulation. of cold water. The box is then closed carefully and introduced into an oven preheated to 70 ⁰ C for 24 hours. The final product is a soft, white paste, characterized by a dry active ingredient content of 25%, and a penetration resistance measured according to the ASTM D 217 standard of 3.11 mm.

The rheology additive in the form of a pre-activated paste is used in the preparation of polymeric MS type mastics.

The storage of the rheology additive is done in the absence of water and moisture to prevent any start of polymerization by crosslinking. The crosslinking reaction (self-crosslinking) occurs at the time of use, in the presence of ambient humidity, at relative humidity (RH)> 50%.

Manufacture of sealants:

Putties are made in the laboratory with a Molteni type device

LABMAX disperser D2 (series 2000). This equipment makes it possible to reproduce the industrial conditions but on a small scale (pilot). It is equipped with a planetary disperser 65 mm in diameter, a squeegee and a vacuum pump which excludes the entry of moisture during manufacture. This device allows the manufacture of 1500 g of product, which is equivalent to three cartridges. The cartridges used are Fischbach E310 HPDE cartridges, 310 ml - accessories KOl - DO 1A0.

The polymeric MS and plasticizer DIUP are mixed at 1000 rpm, at a tangential velocity of 3.5 m. s ¹ , for 5 minutes. The rheology additive is then added and dispersed at 2600 rpm (8.8 m.sup.- ¹ ), the mixture being maintained at a temperature of 30 ^° C. by circulation of water.

Light and UV stabilizers, titanium dioxide and calcium carbonate having previously been dried for 12 hours at 90 ^° C. are incorporated and then dispersed under vacuum at 2600 rpm. The charges are completely dispersed after about an hour.

IV - Characterization methods

The rheological behavior of the compositions comprising at least one additive according to the present invention has been characterized according to the following tests:

1) Extrudability or grammage

1-1) Principle This method is specific to the determination of the extrudability of a single-component sealant from the packaging in which it has been conditioned, the single-component sealant being extruded under compressed air pressure. .

Extrudability is expressed as an extruded weight over a defined time (g.min ¹ ).

1-2) Apparatus

The equipment used is as follows:

- a pneumatic gun for the application of putty on site,

an air compressor with a valve and a manometer to maintain the supply of compressed air at 250 ± 10 KPa (2.5 bars ± 0.1 bar),

a 500 ml plastic cylinder,

- a stopwatch calibrated in seconds,

an extrusion nozzle with a hole diameter of 5 ± 0.3 mm,

- a precision balance to weigh the sample during extrusion. 1-3) Packaging of products

The products to be tested are conditioned for 24 hours in an air-conditioned laboratory at 23 ^° C. and 50% RH, before the start of the test.

1 -4) Product preparation

The end of the threaded bush of a cartridge (Fischbach E310 cartridge: HPDE, 310 ml - KO accessories l - DOlAO) must be cut to form the widest hole possible, with a diameter of at least 6 mm. The extrusion nozzle is then screwed onto the cartridge.

1-5) Rheological characterization procedure

The test is carried out at the temperature of the air-conditioned laboratory (23 ^° C. and 50% RH). Three tests are performed on the same cartridge.

The packaging, prepared as before, is placed in the air gun, then the supply of compressed air is increased up to 250 KPa.

The mastic is extruded from the package into the nozzle, to fill it completely, and thus to free any air possibly enclosed in the package. The gun is then placed vertically above the cylinder itself placed on the scale.

The extrusion and the timer are started simultaneously. About 100 g of mastic are extruded.

Simultaneously again, extrusion and stopwatch are stopped. The test is repeated twice. For each test, the flow rate of the extrusion is calculated in g.min ¹ from the weight of extruded mastic as a function of the extrusion time.

2) Viscosity

Evaluation of the Brookfield ^® viscosity at 23 ° C and 50% RH, with a T-shaped needle No. 95, and at three different speeds: 1, 5 and 10 rpm (or rpm), on a Brookfield ^® viscometer, with Helipath ™ system according to EN ISO 2555.

Brookfield ^® viscosity is expressed in mPa.s. The result is the expression of an average of six values. 3) Thixotropy index

A thixotropy index (V1 / V10) equal to the ratio of the Brookfield ^® viscosity obtained at 1 revolution / min on the Brookfield ^® viscosity obtained at 10 revolutions / min is calculated. This relative and indicative value of thixotropic behavior is commonly used in industry.

4) Consistency

The consistency of the pasta is measured using a texturing apparatus according to ASTM D 217. The standard refers to a standard manual measuring apparatus and has been reproduced by a TAXT2i texture analyzer manufactured by

Thermorheo (supplier: Swantech). The principle of the standard has been automated on the TAXT2i of "Stable Micro System".

4-1) Principle

A suitable cone as described in ASTM D 217 is used with a given force to provide a penetration value into the dough. This "sink" measurement is expressed in millimeters (mm).

The resistance to penetration increases with consistency, and the penetration value decreases with this consistency.

4-2) Apparatus

The equipment used is the following: - an automatic texturometer: TAXT2i, - a cone whose applied force is equivalent to its weight of 47.5 g, with a needle forming an angle of 30 °.

4-3) Packaging of products

The products to be tested must be conditioned in an air-conditioned laboratory under conditions of temperature and humidity of 23 ± 1 ⁰ C and 50 ± 5% RH, for a period of at least 24 hours before the start of the test.

4-4) Product Preparation

The products are packaged after synthesis in 1-liter cans (height: 13 cm, diameter: 11 cm). The texture measurement is carried out after the ripening stage, and before the use of the samples.

4-5) Procedure The test is carried out at the temperature of the air-conditioned laboratory. Three trials are done on a pot.

The sample is placed under the cone, and the tip of the needle is placed on the surface of the dough.

The program on the TAXT2i is then started, and the penetration is triggered.

The value of the displacement of the needle in the dough is then raised. The results are expressed in millimeters (mm).

V - Examples

1) Examples of mastics formulated with the additive in the form of a non-pre-activated composition (reference example) and with the additive in the form of a pre-activated paste (example of the invention) in the DIUP

The reference additive (non-pre-activated composition) and the additive of the invention (pre-activated paste), in the DIUP, were evaluated in the following sealant formulation:

Table 2

Results:

Table 3

2) Examples of sealants with different additives

Four different formulas of mastics were made: Example 1: putty without additive, Example 2: putty with a powder additive Crayvallac® SL,

Example 3 Putty with Pre-Activated Paste in DIUP Example 4 Putty with Pre-Activated Paste in PPG 2000

The 4 examples were carried out according to the formulas indicated in Table 4:

Table 4

^* In the plasticizer (25 wt% polyamide in 75% by weight of plasticizer).

Example 1 (comparative): mastic without additive of rheology

The dispersion is carried out for one hour at 2600 rpm (8.8 m.s.sup.- ¹ ), adiabatically at room temperature. Example 2 (comparative): putty with a Crayvallac ^® SL powder additive

The dispersion is heated for two hours at 80 ^° C.

2600 rpm to activate the powder additive having a maximum particle size of 15 μm.

At the end of the activation, after two hours, the Molteni's speed is lowered to 1500 rpm (5.1 m.s- ¹ ) and the mixture is cooled by circulation of cold water to reach a temperature less than 50 ^° C.

Examples 3 and 4 (invention): putty with a pre-activated paste respectively in the DIUP and in the PPG 2000 (pre-activated pastes described previously in § III a) and b))

The dispersion is for one hour at 2600 rpm, without heating. The addition of n-trimethoxysilane (2-aminoethyl-3-amino) propyl (Dynasylan ^® DAMO) and vinyltrimethoxysilane (Dynasylan ^® VTMO) is at a temperature below 50 ⁰ C to avoid evaporation. When the temperature is less than 5O ⁰ C, the adhesion promoter Dynasylan ^® DAMO and the dehydrating agent Dynasylan ^® VTMO, are added and mixed under vacuum and with gentle stirring at 1000 revolutions / min for 15 min. The catalyst is then added and mixed under vacuum for 10 minutes at

1000 rpm.

The putty is then put into cartridges and then rested for at least 24 hours in an air-conditioned room at 23 ° C.

Results:

Table 5: Consistency

Table 6

Figures:

FIG. 1 shows the evolution of the elastic and viscous modules of the reference examples (non-pre-activated composition) and of the invention (preactivated paste) in the DIUP, as a function of the maturation time.

FIG. 2 shows the evolution of the elastic and viscous modules of the reference examples (non-pre-activated composition) and of the invention (preactivated paste) in the PPG 2000, as a function of the maturation time.

FIG. 3 shows the evolution of the elastic and viscous dynamic modules of the reference examples (non-pre-activated composition) and of the invention (pre-activated paste) in the DIUP, as a function of frequency. FIG. 4 shows the evolution of the elastic and viscous dynamic modules of the reference examples (non-pre-activated composition) and of the invention (pre-activated paste) in the PPG 2000, as a function of frequency.

Claims

1) rheology additive in the form of a pre-activated paste, characterized in that it comprises:

2) Additive according to claim 1, characterized in that the elastic dynamic modulus G 'of said rheology additive in the form of preactivated paste, measured on the mixture A) + B), at a temperature of 23 ° C and at a frequency of 1 Hz, is greater than or equal to 10 ⁴ Pa, preferably greater than or equal to 8.10 ⁴ Pa, and still more preferably greater than or equal to 5.10 ⁵ Pa.

3) Additive according to one of claims 1 or 2, characterized in that said plasticizer is a polar organic plasticizer comprising at least one ether group and / or an ester group and / or an epoxy group.

4) Additive according to one of claims 3, characterized in that said plasticizer comprises at least one ether group, and in that it is selected from polyether homopolymers and / or copolymers of ethylene oxide and / or propylene oxide and / or a mixture of said polyethers and / or their derivatives, these derivatives comprising, inter alia, said polyethers blocked at the end of the chain with a C ₁ to C ₄ alkoxy group or by a C ₂ to C ₄ ester group, said polyethers having a weight average molecular weight Mw ranging from 150 to 6000.

5) Additive according to claim 3, characterized in that said plasticizer comprises at least one ester group, and in that it is chosen from monoesters and / or polyesters, obtained from alcohols C4 to C21, optionally alkoxylated alcohols, and from mono- or polyacids of functionality ranging from 1 to 4, selected from:

organic acids chosen from aromatic acids having a chain length ranging from Ce to C ₁ O, and / or aliphatic acids having a chain length ranging from C ₄ to C ₁ S, or

- mineral acids.

6) Additive according to claim 5, characterized in that said mono- and / or polyesters are esters of: - aromatic acids, chosen from phthalic and trimellitic esters and their respective isomers,

aliphatic acids, chosen from adipic, citric, sebacic and azelaic esters, and

- Of mineral acids, chosen from sulphonic, sulfuric, sulfinic, phosphoric, phosphonic and phosphinic esters.

7) Additive according to claim 3 characterized in that said plasticizer comprises at least one epoxy group chosen from epoxidized oils based on fatty acid.

8) Additive according to one of claims 1 to 7, characterized in that said plasticizer is present in the absence of any other compound selected from alcohols of molecular weight Mw <150, or from polar aprotic solvents chosen from: N-methylpyrrolidone, N-ethylpyrrolidone, N-butylpyrrolidone, acetonitrile, N, N-dimethylformamide, N, N'-dimethylacetamide, dimethylsulfoxide, N, N, N ', N'-tetramethylurea, hexamethylphosphoramide, diiexainethylphosphorous triamide or propylene carbonate.

9) Additive according to claim 4, characterized in that said plasticizer is selected from polypropylene homopolymers of propylene oxide with a weight average molecular weight Mw ranging from 1000 to 3000, and / or their derivatives. 10) Additive according to claim 6, characterized in that said plasticizer comprises at least one aromatic acid ester group C ₈ -C ₁₀ O, selected from mono- and / or di-alkyl phthalates.

1 1) The additive according to claim 10, characterized in that said plasticizer is at least one di-alkylphtalate with said alkyl being the same or different and selected from alkyl, C7-Ci _8.

12) Additive according to claim 1 1, characterized in that said plasticizer is a di-iso-undecylphthalate.

13) Additive according to claim 6, characterized in that said plasticizer is a sulphonic ester selected from alkyl sulphonates C _{1 to} C 21.

14) Additive according to one of claims 1 to 13, characterized in that the maximum penetration value of the final pre-activated paste is less than 15 mm, measured according to ASTM D 217.

15) Additive according to one of claims 14, characterized in that said maximum penetration value is less than 10 mm.

16) Additive according to one of claims 14 or 15, characterized in that said maximum penetration value is less than 5 mm.

17) Additive according to one of claims 1 to 16, characterized in that the weight ratio of said fatty acid diamide ranges from 10 to 40% relative to the mixture A) + B).

18) Additive according to one of claims 1 to 17, characterized in that said fatty acid diamide is obtained by polycondensation between at least one C 2 -C 12 primary diamine and at least one monocarboxylic acid C3 chain length to C22, the reaction product can optionally be diluted in hydrogenated castor oil, and in this case at a rate ranging from 10 to 100% by weight relative to the total diamide + hydrogenated castor oil.

19) Additive according to one of claims 1 to 18, characterized in that it is obtainable by a process comprising the following steps: i) progressive dispersion of said diamide in powder form, in said plasticizer to obtaining a homogeneous dispersion, at controlled ambient temperature, by means of a temperature regulation, ii) maintaining the homogeneous dispersion obtained in step i) in at least one isotherm with a corresponding temperature ranging from 50 to 120 ^° C. C, for a period of 1 to 100 hours.

20) Process for preparing the additive as defined according to one of claims 1 to 19, characterized in that it comprises the following steps: i) progressive dispersion of said diamide in powder form, in the plasticizer to obtaining a homogeneous dispersion, at controlled ambient temperature, by means of a temperature regulation, the diamide and the plasticizer being as defined according to one of claims 1 to 19, ii) maintaining the homogeneous dispersion obtained during step i) in at least one isotherm with a corresponding temperature ranging from 50 to 120 ^° C., for a period of 1 to 100 hours.

21) The method of claim 20 characterized in that at the end of step ii) the maximum penetration value of the formed dough is less than 15 mm, measured according to ASTM D 217.

22) Composition of organic binder or pigment concentrate or fillers, characterized in that it comprises in addition to said binder, pigment or filler, at least one additive as defined according to one of claims 1 to 19, or obtained by a process as defined in one of claims 20 or 21. 23) Composition according to claim 22, characterized in that said additive is present in a content by weight ranging from 1 to 40% relative to the total weight of said composition.

24) Composition according to claim 22 or 23, characterized in that said additive is present in a content by weight ranging from 15 to 30% relative to the total weight of said composition.

25) Composition according to one of claims 22 to 24, characterized in that said additive is present in a content by weight ranging from 10 to 20% relative to the total weight of said composition.

26) Composition according to one of claims 22 to 25, characterized in that said diamide is present as a dry active ingredient at a content in weight ranging from 0.1 to 16%, relative to the total weight of said composition.

An organic binder composition according to one of claims 22 to 26, characterized in that it is a coating, putty, glue, adhesive, sealant, molding, or cosmetic.

28. Organic binder composition according to claim 27, characterized in that it is curable, including self-crosslinkable at room temperature, or non-crosslinkable.

29) Organic binder composition according to claim 28, characterized in that it is a crosslinkable composition single-component or bicomponent.

30) An organic binder composition according to one of claims 22 to 29, characterized in that said organic binder is selected from at least one epoxy-amine reactive system, an unsaturated polyester, a vinylester, an epoxy resin, a reactive silicone resin , an alkyd grafted with a polyester or a polyamide or modified diurea-diurethane, or an ungrafted alkyd, a polyurethane or a silicone, a bi-polyurethane, crosslinkable component, a polysiloxane, a polysulfide polymer, a reactive acrylic polymer, a multifunctional oligomer (meth) acrylate or acrylated acrylic oligomer or allyl multifunctional oligomer, an SBR-type elastomer, polychloroprene or butyl rubber, or a silane prepolymer, preferably a silane polyether or a silane polyurethane, or a silane polyether urethane with -OH or -CO2H function.

31) An organic binder composition according to one of claims 27 to 30, characterized in that it is a sealant, adhesive, adhesive or sealant composition, which is self-crosslinkable, and polyether silane or polyurethane silane base.

32) Organic binder composition according to one of claims 27 to 30, characterized in that it is a protective coating composition and / or decoration and / or surface treatment of various substrates.

33) An organic binder composition according to claim 32, characterized in that said coating composition is a composition of: paints, varnishes, gel coats, inks, or plastisols based on PVC.

34) Process for the preparation of a composition according to one of claims 22 to 33, characterized in that it comprises the following steps: i) addition of an additive as defined according to one of claims 1 to 19 or obtained by a process as defined according to one of claims 20 or 21, in the composition as defined in one of claims 22 to 33, ii) homogenization of the mixture with a kneader and / or planetary mixer and / or disperser at high speed, without having any need, at this stage, to apply an activation treatment.

35) Process for the preparation of a composition according to claim 34, characterized in that it comprises a further preliminary step according to: i) preparation of an additive, as defined according to one of claims 1 to 19, according to the preparation process as defined according to one of claims 20 or 21, ii) adding said additive obtained according to step i ) in said composition, as defined according to one of claims 22 to 33, iii) homogenization of the mixture with a kneader and / or planetary mixer and / or high speed disperser, without having any need, at this stage, of apply an activation treatment.

36) Use of at least one additive as defined according to one of claims 1 to 19 or obtained by the process as defined according to one of claims 20 or 21, or a composition as defined according to one of claims 22 to 33, or obtained by the process as defined according to one of claims 34 or 35, characterized in that it is without the need for activation in situ, by simple addition of said additive and homogenization in the formula final.

37) Use of at least one additive as defined according to one of claims 1 to 19 or obtained by the process as defined in one of claims 20 or 21, or a composition as defined according to one of claims 22 to 33, or obtained by the method as defined in one of claims 34 or 35, characterized in that it is a use in coating applications, or mastics, glues , adhesives, sealants, molding, or in cosmetic applications.

38) Coatings for paints, varnishes, inks or gels coats, or plastisols based on PVC, or putties, or glues, or adhesives, or gaskets, or composites , or molded parts, or SMC / BMC laminates, or cosmetic products, characterized in that they are obtained from at least one additive as defined according to one of claims 1 to 19 or are obtained by the use as defined according to one of claims 36 or 37, or are obtained from an additive obtained by the process as defined according to one of claims 20 or 21, or are obtained from a composition as defined according to one of claims 22 to 33, or from a composition obtained by the process as defined according to one of claims 34 or 35.