Composition comprising a silylated polymer

Abstract

The invention relates to a composition comprising: - a silylated polymer, - carbon black having an oil absorption number (OAN) of at least 80 ml / 100 g, and - a rheology agent. The invention also relates to the use of the composition according to the invention for adhesive bonding and sealing purposes.

Description

[0001] Composition comprising a silylated polymer

[0002] Field of invention

[0003] The present invention relates to a composition comprising a silylated polymer, as well as its use in particular for bonding and sealing.

[0004] Technical background

[0005] Various polymer-based compositions are available on the market, which can be used in many areas, including as sealants. Sealants are used to assemble (or join or bond) two substrates that can be chosen from a wide variety of materials, and can also be used as sealants. Sealants provide the resulting assembly with advantageous mechanical properties of strength, elasticity and / or flexibility, as well as fluid tightness.

[0006] For example, polymer-based compositions can be used as sealants in building construction, shipbuilding, or the transportation sector (e.g., road, maritime, rail, or aerospace).

[0007] Some applications, such as attaching a window (e.g., a windshield or a window) to a vehicle body, require the polymer composition to have specific mechanical properties, particularly high tensile strength and high elongation at break. Indeed, it is essential that the composition does not break when subjected to impacts.

[0008] The compositions on the market for windshield replacement are usually polyurethane-based compositions with isocyanate terminations, which generally have high tensile strength and high elongation at break. At the time of implementation of the composition for the realization of the assembly, the reaction of the isocyanate reactive groups with the water that comes from the humidity of the air and / or the substrates to be assembled, is called crosslinking reaction. It is the completion of this reaction, after a period called crosslinking time, that allows the creation of a solid three-dimensional network, which contributes to giving the adhesive joint thus formed the desired mechanical properties.

[0009] Compositions based on alkoxysilane-terminated polymers (also known as silylated polymers) have the advantage of being free of isocyanates. These compositions therefore constitute a toxicologically preferred alternative to compositions based on isocyanate-terminated polyurethanes.

[0010] The crosslinking reaction of these silylated polymer-based compositions occurs, in the presence of moisture, by hydrolysis of the alkoxysilane groups carried by the polymer, then their condensation to form a siloxane bond (-Si- O— Si— ) which unites the polymer chains into a solid three-dimensional network.

[0011] However, it is difficult to obtain a composition, particularly a sealant, based on silylated polymer having both high tensile strength and high elongation at break. Indeed, compositions based on silylated polymer generally have lower tensile strength and elongation at break than compositions based on polyurethane with isocyanate terminations.

[0012] There is therefore a need to find a composition comprising a silylated polymer having improved tensile strength and elongation at break properties, particularly similar to compositions based on polyurethane with isocyanate ends.

[0013] Summary of the invention

[0014] The present invention relates to a composition comprising: a silylated polymer,

[0015] - carbon black having an oil absorption index (OAN) of at least 80 mL / 100 g, and

[0016] - a rheology agent.

[0017] The present invention also relates to a method of assembling two substrates by gluing, comprising:

[0018] - coating, on at least one of the two substrates to be assembled, the composition according to the invention, as defined previously; then

[0019] - the effective contact of the two substrates.

[0020] The present invention also relates to an article capable of being obtained according to the assembly method as defined above, preferably a vehicle.

[0021] The present invention also relates to a vehicle comprising a composition as defined in the present description, said composition being simultaneously in contact with a first substrate and a second substrate of said vehicle.

[0022] Furthermore, the present invention relates to the use of the composition according to the invention, as a sealant, in particular as a sealing joint.

[0023] Finally, the present invention relates to the use of the composition according to the invention, for bonding and sealing. Surprisingly, it has been found that the addition of a combination of a rheology agent and carbon black having a high OAN in a silylated polymer composition makes it possible to significantly improve both the tensile strength and elongation at break properties of the composition.

[0024] The composition according to the invention is therefore particularly advantageous for fixing a window (for example a windshield or a window) to the bodywork of a vehicle, in particular for replacing the windshield of a vehicle.

[0025] Description of the invention

[0026] Thus, the invention relates to a composition comprising: a silylated polymer,

[0027] - carbon black having an oil absorption index (OAN) of at least 80 mL / 100 g, and

[0028] - a rheology agent.

[0029] By "silylated polymer" is meant a polymer comprising at least one alkoxysilane group. Preferably, the silylated polymer comprises at least one alkoxysilane group at the end of the polymer.

[0030] The silylated polymer is generally in the form of a more or less viscous liquid. Advantageously, the silylated polymer has a viscosity at 23°C ranging from 10 to 200 Pa.s, preferably from 20 to 175 Pa.s, more preferably from 30 to 150 Pa.s, even more preferably from 45 to 125 Pa.s.

[0031] The viscosity of the silylated polymer can for example be measured using a Brookfield-type method at 23°C and 50% relative humidity (S28 needle).

[0032] Within the scope of the invention, the ranges of values ​​are understood to include the limits. For example, the range “between 0% and 25%” includes in particular the values ​​0% and 25%.

[0033] Advantageously, the silylated polymer comprises at least one, preferably at least two, alkoxysilane groups of formula (I):

[0034] -IF(R4) p (GOLD 5 )3i> (I) in which:

[0035] - R 4 represents a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, and when p is equal to 2, the radicals R 4 are the same or different, - R 5 represents a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, and when p is equal to 0 or 1, the radicals R 5 are identical or different, two OR groups 5 which can be engaged in the same cycle, and

[0036] - p is an integer equal to 0, 1 or 2, preferably equal to 0 or 1.

[0037] Preferably, the alkoxysilane groups of the silylated polymer are of formula (I) with:

[0038] - R 4 and R 5 each represent a methyl radical, and

[0039] - p is equal to 0 or 1.

[0040] Advantageously, the silylated polymer has a number-average molar mass of between 500 g / mol and 70,000 g / mol, preferably between 4,000 g / mol and 60,000 g / mol, more preferably between 10,000 g / mol and 50,000 g / mol.

[0041] The molar mass of polymers can be measured by methods well known to those skilled in the art, for example by NMR or by size exclusion chromatography using polystyrene-type standards.

[0042] Advantageously, the silylated polymer is of formula (II), (III) or (IV): in which:

[0043] - R 4 , R5 and p have the same meaning as in formula (I) described above,

[0044] - P represents a saturated or unsaturated polymeric radical, with a linear or branched open chain, or comprising one or more optionally aromatic cycles, optionally comprising one or more heteroatoms, such as oxygen, nitrogen, sulfur and / or silicon, preferably oxygen and / or nitrogen, and optionally comprising one or more ionic groups,

[0045] - R 1 represents a divalent hydrocarbon radical comprising from 5 to 15 carbon atoms, saturated or unsaturated, with a linear or branched open chain, or comprising one or more optionally aromatic cycles, R 3 represents a linear or branched divalent alkylene radical comprising from 1 to 6 carbon atoms, preferably from 1 to 3 carbon atoms,

[0046] - X represents a divalent radical chosen from -NH-, -NR 7 - or -S-,

[0047] - R 7 represents a linear or branched alkyl radical comprising from 1 to 20 carbon atoms and which may also comprise one or more heteroatoms,

[0048] - f is an integer ranging from 1 to 6, advantageously from 2 to 5, preferably from 2 to 4, even more preferably from 2 to 3.

[0049] Advantageously, the silylated polymer is of formula (II), (III) or (IV) with P representing a polymer radical chosen from polyethers, polycarbonates, polyesters, polyolefins, polyacrylates, polyether polyurethanes, polyester polyurethanes, polyolefin polyurethanes, polyacrylate polyurethanes, polycarbonate polyurethanes, polyether / polyester block polyurethanes and polysiloxanes, preferably chosen from polyethers, polyurethanes and their mixtures, more preferably from polyethers.

[0050] Preferably, the silylated polymer is of formula (IT), (II”), (III') or (IV'): in which:

[0051] R 1 , R 3 , R 4 , R 5 , X, R 7 and p have the same meaning as in formulas (II), (III) and (IV),

[0052] - R 2 represents a saturated or unsaturated, linear or branched, divalent hydrocarbon radical optionally comprising one or more heteroatoms, such as oxygen, nitrogen, sulfur, silicon, and optionally comprising one or more ionic groups,

[0053] - n is an integer, preferably n is such that the number-average molar mass of the silylated polymer is between 500 g / mol and 70,000 g / mol, more preferably between 4,000 g / mol and 60,000 g / mol, even more preferably between 10,000 g / mol and 50,000 g / mol.

[0054] In the silylated polymers of formulas (IT), (II”), (III') or (IV') defined above, when the radical R 2comprises one or more heteroatoms, said heteroatom(s) are not present at the end of the chain. In other words, the free valences of the divalent radical R 2 linked to the neighboring oxygen atoms of the silylated polymer, each come from a carbon atom. Thus, the main chain of the radical R 2 is terminated by a carbon atom at each of the two ends, said carbon atom then having a free valence.

[0055] According to one embodiment, the silylated polymers are obtained from polyols chosen from polyether polyols, polyester polyols, polycarbonate polyols, polyacrylate polyols, polysiloxane polyols, polyolefin polyols and mixtures thereof, preferably from diols chosen from polyether diols, polyester diols, polycarbonate diols, polyacrylate diols, polysiloxane diols, polyolefin diols and mixtures thereof, more preferably from polyether diols. In the case of the polymers of formulas (IT), (II”), (III') or (IV') described above, such diols may be represented by the formula HO-R 2 - OH or H-[O- R 2 ] n -OH, where R 2 has the same meaning as in formulas (IT), (II”), (III') or (IV').

[0056] In particular, in the silylated polymer of formula (IV') defined above, the radical R 2may be the same or different, i.e. the silylated polymer of formula (IV') may be a silylated copolyurethane obtained from HO-R diols 2 -OH same or different.

[0057] According to one embodiment, when the silylated polymer is of formula (II') or (IV'), the radical R 2 can be chosen from the following divalent radicals whose formulas below show the two free valencies:

[0058] - derived from a polypropylene glycol: - derived from a polyester diol

[0059] - derivative of a polybutadiene diol:

[0060] - derivative of a polyacrylate diol:

[0061] - derived from a polysiloxane diol: in which:

[0062] - q represents an integer such as the molar mass in number of the radical R 2ranges from 100 g / mol to 48600 g / mol, preferably from 300 g / mol to 18600 g / mol, more preferably from 500 g / mol to 12600 g / mol,

[0063] - r and s represent zero or a non-zero integer such that the number-average molar mass of the radical R 2 ranges from 100 g / mol to 48600 g / mol, preferably from 300 g / mol to 18600 g / mol, more preferably from 500 g / mol to 12600 g / mol, it being understood that the sum r+s is different from zero,

[0064] - Q 1 represents a linear or branched, saturated or unsaturated, aromatic or aliphatic divalent alkylene radical, preferably having from 1 to 18 carbon atoms, more preferably from 1 to 8 carbon atoms,

[0065] - Q 2 represents a linear or branched divalent alkylene radical preferably having from 2 to 36 carbon atoms, more preferably from 1 to 8 carbon atoms,

[0066] - Q 3 , Q 4 , Q 5 , Q 6 , Q 7and Q 8 , represent, independently of one another, a hydrogen atom or an alkyl, alkenyl or aromatic radical, preferably having from 1 to 12 carbon atoms, preferably from 2 to 12 carbon atoms, more preferably from 2 to 8 carbon atoms.

[0067] According to a particular embodiment, when the silylated polymer is of formula (IV'), the silylated polymer can be obtained from HO-R diols 2 -OH different, in which a radical R 2 may be chosen from the above divalent radicals (derived from a polypropylene glycol, a polyester diol, a polybutadiene diol, a polyacrylate diol, a polysiloxane diol) and in which a radical R 2 is the divalent ionic radical of formula: in which:

[0068] - x and y, identical or different, are integers ranging from 1 to 8,

[0069] - z is an integer ranging from 0 to 8,

[0070] - R° represents a hydrogen atom or an alkyl radical comprising from 1 to 18 carbon atoms, and

[0071] - R, R' and R", which may be identical or different, each represent a saturated, unsaturated or aromatic hydrocarbon radical, optionally comprising a heteroatom chosen from N, O and S; R, R' and R" being further such that the tertiary amine of formula N(R)(R')(R") is a linear, branched or cyclic amine or polyamine whose number-average molar mass Mn ranges from 59 to 6000 g / mol and which has a pKa greater than 8.

[0072] According to one embodiment, R 1 is chosen from the following divalent radicals whose formulas below show the two free valences: a) the divalent radical derived from isophorone diisocyanate ( I PDI): b) the divalent radical derived from dicyclohexylmethane diisocyanate (H12MDI): c) divalent radicals derived from the 2,4- and 2,6- isomers of toluene diisocyanate (TDI): d) divalent radicals derived from the 4,4' and 2,4'- isomers of diphenylmethane diisocyanate (MDI): e) the divalent radical derived from hexamethylene diisocyanate (HDI): -(CH2)6- f) the divalent radical derived from m-xylylene diisocyanate (m-XDI):

[0073] According to a preferred embodiment, the silylated polymer is of formula (II”) or (III'), preferably (III'), and the radical R 2 preferably represents a linear or branched divalent alkylene radical comprising from 2 to 4 carbon atoms, more preferably a linear or branched divalent alkylene radical comprising 3 carbon atoms, even more preferably an isopropylene radical (of formula -CH2-CH(CH3)-).

[0074] According to a particularly preferred embodiment, the silylated polymer is a polymer of formula (III') in which:

[0075] - R 2 represents an isopropylene radical,

[0076] - R 4 and R 5 each represent a methyl radical, and

[0077] - p is equal to 1.

[0078] The polymers of formula (II), (II') or (II”) can be obtained according to a process described for example in documents EP 2336208 and WO 2009 / 106699. Among the polymers corresponding to formula (II), mention may be made of:

[0079] - GENIOSIL® STP-E10 (available from WACKER-CHEMIE): polyether of formula (II”) comprising two groups of formula (I) of the dimethoxy type (p equal to 1 and R 4 and R 5 represent a methyl group) having a number-average molar mass of 8889 g / mol where R 3 represents a methyl group;

[0080] - GENIOSIL® STP-E30 (available from WACKER-CHEMIE): polyether of formula (II”) comprising two groups of formula (I) of the dimethoxy type (p equal to 1 and R 4 and R 5 represent a methyl group) having a number-average molar mass of 14493 g / mol where R 3 represents a methyl group;

[0081] DESMOSEAL® S XP 2636 (available from BAYER): polyurethane comprising two groups of formula (I) of the trimethoxy type (p equal to 0 and R 5 represents a methyl group) having a number-average molar mass of 15038 g / mol where R 3 represents an n-propylene group.

[0082] The polymers of formula (III) or (III') can be obtained by hydrosilylation of polyether diallyl ether according to a process described for example in document EP 1829928. Among the polymers corresponding to formula (III), mention may be made of:

[0083] - the MS SAX® 350 polymer (available from KANEKA) corresponding to a polyether comprising two groups of formula (I) of the dimethoxy type (p equal to 1 and R 4 and R 5 represent a methyl group) having a number-average molar mass ranging from 14000 to 16000 g / mol;

[0084] - the MS SAX® 260 polymer (available from KANEKA) corresponding to a polyether comprising two groups of formula (I) of dimethoxy type (p equal to 1, R 4 and R 5 represent a methyl group) having a number-average molar mass of 16000 to 18000 g / mol where R 3 represents an ethyl group;

[0085] - the MS S303H polymer (available from KANEKA) corresponding to a polyether comprising two groups of formula (I) of dimethoxy type (p is equal to 1 and R 4 represents a methyl group) having a number-average molar mass of 21000 to 23000 g / mol;

[0086] - the MS SAX® 725 polymer (available from KANEKA) corresponding to a polyether (R 2 represents an isopropylene radical) comprising two groups of formula (I) of dimethoxy type (p is equal to 1, R 4 and R 5 represent a methyl group) having a number-average molar mass of approximately 41 kg / mol.

[0087] The polymers of formula (IV) or (IV') may for example be obtained by reaction of polyol(s) with one or more diisocyanate(s) followed by a reaction with aminosilanes or mercaptosilanes. A process for preparing polymers of formula (IV) or (IV') is described for example in document EP 2583988. A person skilled in the art will be able to adapt the manufacturing process described in this document in the case of the use of different types of polyols. Among the polymers corresponding to formula (IV), mention may be made of:

[0088] SPLIR+® 1050MM (available from MOMENTIVE): polyurethane comprising two groups of formula (I) of the trimethoxy type (p equal to 0 and R 5 represents a methyl group) having a number-average molar mass of 16393 g / mol where R 3 represents an n-propyl group;

[0089] SPLIR+® Y-19116 (available from MOMENTIVE): polyurethane comprising two groups of formula (I) of the trimethoxy type (p equal to 0 and R 5 represents a methyl group) having a number-average molar mass ranging from 15000 to 17000 g / mol g / mol where R 3 represents an n-propyl group.

[0090] The content of silylated polymer in the composition according to the invention may range from 5% to 60% by weight relative to the total weight of the composition, preferably from 10% to 55% by weight, more preferably from 20% to 50% by weight, even more preferably from 30% to 45% by weight, in particular from 35% to 40% by weight.

[0091] Carbon black

[0092] The carbon black in the composition according to the invention has an oil absorption index (OAN) of at least 80 mL / 100 g.

[0093] The OAN of a carbon black corresponds to the volume in mL of dibutyl phthalate (DBP) oil absorbed by 100 g of carbon black

[0094] For example, OAN can be measured according to ASTM D-2414 and using DBP oil.

[0095] Unless otherwise indicated, the standards referred to throughout the application are those in effect on the date the application was filed.

[0096] The carbon black used in the present invention is generally called “structural” carbon black, and is distinguished from carbon blacks generally used as pigments, in particular by its high OAN.

[0097] Indeed, the carbon blacks used as pigments are of lower quality and have a lower OAN than the carbon black used in the present invention.

[0098] An example of carbon black used as a pigment is PRINTEX® 25 (marketed by Orion), which has an OAN of 45 mL / 100 g. Examples of carbon black that can be used in the present invention are ELFTEX® S7100 and ELFTEX® S5100 (marketed by CABOT), having an OAN of about 117 and 108 mL / 100 g, respectively.

[0099] By "about X", we mean more or less 10% of the value of X.

[0100] Preferably, the OAN of the carbon black is at least 90 mL / 100 g, more preferably at least 100 mL / 100 g, even more preferably at least 110 mL / 100 g.

[0101] Advantageously, the carbon black content in the composition according to the invention is at least 2% by weight relative to the total weight of the composition, preferably from 3% to 20% by weight, more preferably from 5% to 18% by weight, even more preferably from 6% to 15% by weight, for example 6%.

[0102] The rheology agent makes it possible to adjust the rheological properties of the composition according to the invention.

[0103] As an example, any rheology agent commonly used in the field of putty compositions can be cited.

[0104] Advantageously, the rheology agent is one or more thixotropic agents, the thixotropic agents being for example solid at 23°C and / or having a viscosity at 23°C greater than 200 mPa.s according to ISO 12058-1, preferably solid at 23°C. A thixotropic agent generally influences the thixotropy of a composition. Thixotropy is the property of certain compositions to become less viscous when a constant force (for example, constant stress shear) is applied and, after stopping the stress, the viscosity returns to its initial state after an appropriate period of time. The higher the force, the more the viscosity decreases.

[0105] In particular, one or more rheology agents chosen from:

[0106] - PVC plastisols, corresponding to a suspension of PVC in a plasticizing agent miscible with PVC, obtained in situ by heating at temperatures ranging from 60°C to 80°C. These plastisols may be those described in particular in the work “Polyurethane Sealants”, Robert M. Evans, ISBN 087762-998-6;

[0107] - fumed silica, such as HDK® N20 marketed by WACKER;

[0108] - urea derivatives resulting from the reaction of an aromatic diisocyanate monomer such as 4,4'-MDI with an aliphatic amine such as butylamine. The preparation of such urea derivatives is described in particular in application FR 1 591 172;

[0109] - waxes derived from castor oil, such as THIXCIN® R available from ELEMENTIS,

[0110] - amide waxes, preferably micronized, such as CRAYVALLAC® SLX, CRAYVALLAC® SLW or CRAYVALLAC® SUPER marketed by Arkema, or THIXATROL® AS8053 or THIXATROL® MAX (EC No.: 432-430-3) which are available from ELEMENTIS, or RHEOBYK 7503 marketed by BYK.

[0111] These rheology agents are thixotropic agents.

[0112] Castor oil-derived waxes mean waxes obtained from castor oil, particularly hydrogenated castor oil. Castor oil-derived waxes are solid at 23°C.

[0113] By "amide waxes" is meant waxes comprising one or more compounds having at least one amide group. In particular, amide waxes can be obtained from fatty acid(s) (e.g. ricinoleic acid) and (di)amine(s). Amide waxes are solid at 23°C.

[0114] Preferably, the rheology agent is an amide wax and / or a wax derived from castor oil, more preferably an amide wax.

[0115] The amide waxes are preferably micronized, that is to say they have an average particle size of less than 1 mm. Advantageously, the amide waxes have an average particle size of less than 500 pm, preferably less than 100 pm, more preferably less than 10 pm.

[0116] The average particle size corresponds advantageously to the d50 particle size, i.e. the maximum size of 50% of the smallest particles by volume, and can be measured with a particle size analyzer, in particular by laser diffraction on a MALVERN type device (for example according to standard NF ISO 13320).

[0117] The amide wax type rheology agents may be heat activatable, i.e. a temperature above room temperature (23°C) may be necessary to activate it (in particular, to activate its rheological properties, in particular thixotropic), during the preparation of the composition according to the invention.

[0118] The activation temperature depends on the rheology agent.

[0119] For example, THIXATROL® AS8053 generally activates at a temperature between 50°C and 55°C, and CRAYVALLAC® SLX generally activates at a temperature between 75°C and 80°C. Advantageously, the content of rheology agent in the composition according to the invention ranges from 0.2% to 20% by weight relative to the total weight of the composition, preferably from 1% to 10% by weight, more preferably from 1% to 5% by weight.

[0120] Membership Promoter

[0121] The composition according to the invention may further comprise at least one adhesion promoter.

[0122] Advantageously, the adhesion promoter is chosen from amino-, mercapto- and epoxy-alkoxysilanes, preferably chosen from aminoalkoxysilanes, more preferably from aminotrialkoxysilanes, even more preferably from aminotrimethoxysilanes.

[0123] An example of an epoxy-alkoxysilane is (3-Glycidyloxypropyl)trimethoxysilane (also called GLYMO).

[0124] Advantageously, the aminotrimethoxysilanes are formed by the group consisting of 4-amino-3,3-dimethylbutyltrimethoxysilane (for example SILQUEST A-LINK 600 marketed by MOMENTIVE), (3-aminopropyl)trimethoxysilane (for example DYNASYLAN® AMMO marketed by EVONIK) and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (for example DYNASYLAN® DAMO or DAMO-T marketed by EVONIK). Preferably, the aminotrimethoxysilanes are formed by the group consisting of 4-amino-3,3-dimethylbutyltrimethoxysilane and (3-aminopropyl)trimethoxysilane.

[0125] Advantageously, the composition according to the invention comprises at least one adhesion promoter.

[0126] According to a preferred embodiment, the at least one adhesion promoter is a mixture of at least two adhesion promoters, preferably two adhesion promoters.

[0127] According to this preferred embodiment, the adhesion promoters are chosen from aminoalkoxysilanes, preferably from aminotrialkoxysilanes, more preferably from aminotrimethoxysilanes. Preferably, the adhesion promoter is a mixture of two adhesion promoters chosen from 4-amino-3,3-dimethylbutyltrimethoxysilane, (3-aminopropyl)trimethoxysilane and n-butyl-3-aminopropyl-trimethoxysilane. More preferably, the adhesion promoter is a mixture of 4-amino-3,3-dimethylbutyltrimethoxysilane and (3-aminopropyl)trimethoxysilane.

[0128] According to a preferred embodiment in which the adhesion promoter is a mixture of two adhesion promoters, the weight ratio (1 er membership promoter) / (2 nd adhesion promoter) is advantageously between 0.25 and 4, preferably between 0.5 and 2, more preferably between 0.7 and 1.5, for example equal to 1.

[0129] The content of adhesion promoter(s) in the composition according to the invention may range from 0.2% to 5% by weight relative to the total weight of the composition, preferably from 0.5% to 3% by weight, more preferably from 1.0% to 2.0% by weight.

[0130] Advantageously, the composition according to the invention further comprises a filler.

[0131] Preferably, the filler is chosen from mineral fillers, organic fillers and their mixtures, more preferably from mineral fillers.

[0132] Advantageously, the mineral fillers are formed by the group consisting of clay, quartz, hollow mineral microspheres and carbonate fillers.

[0133] Among the hollow mineral microspheres, we can cite hollow glass microspheres, and more particularly those made of sodium and calcium borosilicate or aluminosilicate.

[0134] Preferably, the mineral fillers are formed by the group consisting of carbonate fillers.

[0135] According to a preferred embodiment, the composition according to the invention further comprises a carbonated filler, advantageously the carbonated filler is chosen from alkali or alkaline earth metal carbonates and their mixtures, preferably the carbonated filler comprises calcium carbonate, more preferably the carbonated filler is chalk or calcium carbonate coated with fatty acids, even more preferably precipitated calcium carbonate coated with fatty acids.

[0136] When calcium carbonate is coated with fatty acids, this makes the calcium carbonate particles completely or partially hydrophobic. In addition, the fatty acid coating acts as a hydrophobic coating that can prevent the calcium carbonate from absorbing the components of the composition and rendering them ineffective. The hydrophobic coating of the calcium carbonate can represent from 0.1% to 3.5% by weight, based on the total weight of calcium carbonate. Preferably, the fatty acids coating the calcium carbonate comprise or consist of more than 50% by weight of stearic acid based on the total weight of the fatty acids.

[0137] Examples of calcium carbonate coated with non-precipitated fatty acids include OMYACARB 2T-AV or OMYA BLH (marketed by OMYA), or CALATEM C16T (marketed by Provençale).

[0138] Examples of precipitated calcium carbonate coated with fatty acids include HAKUENKA® CCR-S10 (marketed by OMYA) or CALOFORT® (marketed by Specialty Minerals).

[0139] Advantageously, the organic fillers are formed by the group consisting of polyvinyl chloride (PVC), polyolefins, rubber, ethylene vinyl acetate (EVA), expandable or non-expandable thermoplastic polymer hollow microspheres (such as vinylidene chloride / acrylonitrile hollow microspheres) and aramid fibers (such as Kevlar®), preferably PVC.

[0140] Advantageously, the average particle size of the filler is between 10 nm and 400 pm, preferably between 20 nm and 100 pm, more preferably between 30 nm and 1 pm, even more preferably between 40 nm and 300 nm.

[0141] The average particle size corresponds advantageously to the d50 particle size, i.e. the maximum size of 50% of the smallest particles by volume, and can be measured with a particle size analyzer, in particular by laser diffraction on a MALVERN type device (for example according to standard NF ISO 13320).

[0142] Advantageously, the filler content ranges from 10% to 80% by weight relative to the total weight of the composition, preferably from 20% to 60% by weight, more preferably from 30% to 50% by weight, even more preferably from 35% to 40% by weight.

[0143] Crosslinking catalyst

[0144] The composition according to the invention may further comprise a crosslinking catalyst.

[0145] The crosslinking catalyst may be any catalyst known to those skilled in the art for silanol condensation. Examples of such catalysts include:

[0146] - organic titanium derivatives such as titanium acetyl acetonate (for example TYZOR® AA75 marketed by Dorf Ketal), - aluminum such as aluminum chelate (for example K-KAT® 5218 marketed by KING INDUSTRIES),

[0147] - amines such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), diethyl ether-2,2'-morpholine (DMDEE), 1,4-diazabicylo[2.2.2]octane (DABCO),

[0148] - catalysts based on zinc carboxylate and DBU (for example K-KAT® 670 marketed by KING INDUSTRIES),

[0149] - tin-based catalysts such as compounds derived from dioctyltin or dibutyltin; in particular dioctyltin oxide, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dicarboxylate, dibutyltin diacetylacetonate (DBTDAA), dibutyltin dilaurate (DBTDL), dibutyltin diacetate or dibutyltin oxide, preferably dioctyltin or dibutyltin oxide. Examples include NEOSTANN® S-1 (marketed by KANEKA), or TIB KAT® 425 or TIB KAT® 423 (marketed by TIB CHEMICALS),

[0150] - guanidine derivatives such as 1-(o-tolyl)biguanide (CAS No.: 93-69-6), for example RHENOCURE 1000 C (marketed by RheinChemie Additives).

[0151] Preferably, the crosslinking catalyst is a tin-based catalyst, preferably chosen from compounds derived from dioctyltin and dibutyltin, more preferably from dioctyltin or dibutyltin oxide.

[0152] The content of crosslinking catalyst in the composition according to the invention may range from 0.01% to 5% by weight relative to the total weight of the composition, preferably from 0.02% to 2% by weight, more preferably from 0.05% to 1% by weight, even more preferably from 0.1% to 0.8% by weight.

[0153] The composition according to the invention may also further comprise a crosslinking cocatalyst. Advantageously, the crosslinking cocatalyst is an organic polyester derived from silicic acid, i.e. an organic compound derived from silicic acid comprising at least two alkoxysilane functions. Examples that may be mentioned include tetraethoxysilane (for example WACKER® TES 28 or TES 40 WN) or 1,2-bis(triethoxysilyl)ethane (for example Dynasylan® BTSE).

[0154] The content of crosslinking cocatalyst in the composition according to the invention may range from 0.01% to 5% by weight relative to the total weight of the composition, preferably from 0.05% to 2% by weight, more preferably from 0.1% to 1% by weight.

[0155] Other additives The composition according to the invention may further comprise at least one additive chosen from plasticizers, moisture absorbers, solvents, UV stabilizers and mixtures thereof.

[0156] Advantageously, the composition according to the invention comprises a mixture of additives chosen from plasticizers, moisture absorbers, solvents and UV stabilizers (or antioxidants).

[0157] The total content of additives in the composition according to the invention may range from 0.5% to 30% by weight relative to the total weight of the composition, preferably from 5% to 25% by weight, more preferably from 10% to 20% by weight.

[0158] Advantageously, the composition according to the invention comprises a plasticizer. A plasticizer is different from a rheology agent because the properties of a composition comprising a plasticizer will be identical under the application of a stress (such as shear) or in the absence of stress. In contrast, the properties of a composition comprising a rheology agent will be different if a stress is applied. A plasticizer can be used to adjust the viscosity (such as a solvent).

[0159] The plasticizer can be any plasticizer commonly used in the field of putty compositions.

[0160] Preferably, the plasticizer is chosen from:

[0161] - diisodecyl phthalate (for example PALATINOL® DIDP marketed by BASF),

[0162] - diisononyl phthalate (DINP) (for example PALATINOL® N marketed by BASF),

[0163] - an ester of alkylsulfonic acid and phenol (for example MESAMOLL® marketed by LANXESS),

[0164] - the diisononyl ester of 1,2-cyclohexanedicarboxylic acid (for example HEXAMOLL DINCH® marketed by BASF), and

[0165] - pentaerythritol tetravalerate (for example PEVALEN™ marketed by PERSTORP).

[0166] More preferably, the plasticizer is the diisononyl ester of 1,2-cyclohexanedicarboxylic acid.

[0167] Advantageously, the plasticizer content ranges from 2% to 25% by weight relative to the total weight of the composition, preferably from 5% to 20% by weight, more preferably from 7% to 15% by weight.

[0168] The composition according to the invention may comprise from 0% to 5% by weight of a solvent relative to the total weight of the composition, preferably a solvent that is volatile at room temperature (temperature of the order of 23°C). The volatile solvent may, for example, be chosen from alcohols that are volatile at room temperature, such as ethanol or isopropanol. The volatile solvent makes it possible, for example, to reduce the viscosity of the composition and make the composition easier to apply. The volatile nature of the solvent allows the seal, obtained after the composition has hardened, to no longer contain any solvent. Thus, the solvent, for example, has no negative influence on the hardness of the seal.

[0169] Advantageously, the composition according to the invention comprises up to 3.5% by weight of a moisture absorber, relative to the total weight of the composition, which may be chosen from vinyltrimethoxysilane (for example DYNASYLAN® VTMO marketed by EVONIK), propyltrimethoxysilane (for example DYNASYLAN® PTMO marketed by EVONIK), vinyltriethoxysilane (VTEO), alkoxyarylsilanes (for example GENIOSIL® XL 70 marketed by WACKER), p-toluenesulfonyl isocyanate (PTSI) and calcium oxide.

[0170] Preferably, the moisture absorber is chosen from vinyltrimethoxysilane, vinyltriethoxysilane and alkoxyarylsilanes, more preferably vinyltrimethoxysilane.

[0171] Advantageously, the composition according to the invention comprises up to 1% by weight of one or more UV stabilizers (or antioxidants) relative to the total weight of the composition. UV stabilizers are typically introduced to protect the composition from degradation resulting from a reaction with oxygen which is likely to form by the action of heat or light. These compounds may include antioxidants capable of trapping free radicals.

[0172] Advantageously, the UV stabilizer(s) (or antioxidants) are chosen from benzotriazoles, benzophenones, phenols and so-called hindered amines such as bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate (CAS No.: 41556-26-7), methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate (CAS No.: 82919-37-7), octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 4,4'-bis(a,a-dimethylbenzyl)diphenylamine, and mixtures thereof. Examples include IRGANOX 1076, TINUVIN® 292, TINUVIN® 765 or TINUVIN® 770 DF products marketed by BASF, RIASORB UV-123 marketed by RIANLON, AddWorks® IBC 760 marketed by CLARIANT and OKABEST CLX 50 marketed by OKA.Preferably, the UV stabilizer(s) (or antioxidants) are chosen from so-called hindered phenols and amines such as bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 4,4'-bis(a,a-dimethylbenzyl)diphenylamine, and mixtures thereof.

[0173] According to one embodiment, the UV stabilizers (or antioxidants) are a mixture of bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2, 2,6,6-tetramethyl-4-piperidyl)sebacate, octadecyl 3-(3,5-di-tetrabutyl-4-hydroxyphenyl)propionate and 4,4'-bis(a,a-dimethylbenzyl)diphenylamine.

[0174] Other characteristics of the composition according to the invention

[0175] According to one embodiment, the composition according to the invention comprises:

[0176] - from 5% to 60% by weight of silylated polymer, relative to the total weight of the composition,

[0177] - at least 3% by weight of carbon black having an OAN of at least 80 mL / 100 g, relative to the total weight of the composition,

[0178] - from 0.2% to 20% by weight of rheology agent (advantageously, thixotropic agent), relative to the total weight of the composition,

[0179] - from 0.2% to 5% by weight of adhesion promoter(s), relative to the total weight of the composition,

[0180] - from 10% to 80% by weight of filler, relative to the total weight of the composition,

[0181] - from 0.01% to 5% by weight of crosslinking catalyst, relative to the total weight of the composition,

[0182] - optionally from 0.01% to 5% by weight of crosslinking cocatalyst relative to the total weight of the composition, and

[0183] - from 0.5% to 30% by weight of one or more additives chosen from plasticizers, moisture absorbers, solvents and UV stabilizers, relative to the total weight of the composition.

[0184] Preferably, the composition according to the invention consists essentially of the ingredients mentioned above. By "consisting essentially", it is meant that the composition according to the invention comprises less than 5% by weight of ingredients other than the aforementioned ingredients, relative to the total weight of the composition, preferably less than 2% by weight, even more preferably less than 1% by weight. The ingredients of this embodiment and their particular contents are as described above, including the embodiments.

[0185] According to a particular embodiment, the composition according to the invention comprises:

[0186] - from 35% to 40% by weight of silylated polymer, relative to the total weight of the composition, the silylated polymer preferably being a polymer of formula (III'),

[0187] - from 6% to 15% by weight of carbon black, relative to the total weight of the composition, said carbon black having an OAN of at least 80 mL / 100 g, preferably at least 110 mL / 100 g,

[0188] - from 1% to 5% by weight of rheology agent, relative to the total weight of the composition, the rheology agent being an amide wax,

[0189] - from 1.0% to 2.0% by weight of adhesion promoters, relative to the total weight of the composition, the adhesion promoters being chosen from aminotrimethoxysilanes,

[0190] - from 35% to 40% by weight of filler, relative to the total weight of the composition, the filler being precipitated calcium carbonate coated with fatty acids,

[0191] - from 0.1% to 0.8% by weight of crosslinking catalyst, relative to the total weight of the composition, the crosslinking catalyst being a tin-based catalyst,

[0192] - optionally from 0.1% to 1% by weight of crosslinking cocatalyst relative to the total weight of the composition, the crosslinking cocatalyst being an organic polyester derived from silicic acid, and

[0193] - from 10% to 20% by weight of one or more additives chosen from plasticizers, moisture absorbers, solvents and UV stabilizers, relative to the total weight of the composition.

[0194] Preferably, the composition according to the invention consists essentially of the ingredients mentioned above.

[0195] The ingredients of this embodiment and their particular contents are as described above, including the embodiments.

[0196] Advantageously, the composition according to the invention has a tensile strength (often abbreviated TS) greater than or equal to 3.5 MPa, preferably greater than or equal to 4 MPa, more preferably greater than or equal to 4.2 MPa, even more preferably greater than or equal to 4.4 MPa. Advantageously, the composition according to the invention has an elongation at break greater than 210%, preferably greater than or equal to 300%, more preferably greater than or equal to 400%, even more preferably greater than or equal to 500%.

[0197] According to a preferred embodiment, the composition according to the invention has a tensile strength greater than or equal to 3.5 MPa and an elongation at break greater than 210%, preferably a tensile strength greater than or equal to 4 MPa and an elongation at break greater than or equal to 300%, more preferably a tensile strength greater than or equal to 4.2 MPa and an elongation at break greater than or equal to 400%, even more preferably a tensile strength greater than or equal to 4.4 MPa and an elongation at break greater than or equal to 500%.

[0198] The skilled person knows how to determine the tensile strength and elongation at break of a composition. For example, the tensile strength and elongation at break can be measured in accordance with ISO 37 (December 2005), preferably at a constant speed of 500 mm / min.

[0199] In particular, tensile strength and elongation at break can be measured as described in Example 1 below.

[0200] Preparation of the composition according to the invention

[0201] The composition according to the invention can be prepared by simply mixing its ingredients.

[0202] According to a preferred embodiment, the composition according to the invention is prepared according to the following process:

[0203] 1) the silylated polymer is mixed, in a suitable container, with any liquid additives such as plasticizer, solvent, moisture absorber and UV stabilizer (or antioxidant), preferably at a temperature between 18°C ​​and 28°C and at atmospheric pressure, then

[0204] - 2) the carbon black having an OAN of at least 80 mL / 100 g, and any other solid ingredients such as the rheology agent, the filler and solid additives such as a UV stabilizer (or antioxidant) are dispersed in the previous liquid mixture, for the time necessary to obtain a homogeneous mixture, then

[0205] - 3) the remainder of any other liquid ingredients, such as adhesion promoter and catalyst, are added and the medium is homogenized. Preferably, step 2) is carried out at a pressure below atmospheric pressure, more preferably at a pressure below 50 kPa, even more preferably at a pressure below 20 kPa.

[0206] Preferably, step 2) is carried out at a temperature above 30°C, more preferably above 40°C. When the composition according to the invention comprises a heat-activatable rheology agent, the mixture of solid ingredients is advantageously carried out at a temperature at which the rheology agent is activated.

[0207] Preferably, step 3) is carried out at a pressure and temperature approximately equal to those carried out in step 2).

[0208] An example of preparation of the composition according to the invention is described in Example 2.

[0209] Other objects of the present invention

[0210] The present invention also relates to a method of assembling two substrates by gluing, comprising:

[0211] - coating, on at least one of the two substrates to be assembled, the composition according to the invention, as defined previously; then

[0212] - the effective contact of the two substrates.

[0213] The substrates concerned are very varied, and are preferably chosen from concrete, a metal such as aluminum and / or steel and glass.

[0214] According to a preferred embodiment, one of the substrates is steel (for example, a part of a vehicle body) and the other substrate is glass (for example, a window such as a windshield or a window).

[0215] The present invention also relates to an article capable of being obtained according to the assembly method as defined above, preferably a vehicle.

[0216] The present invention also relates to a vehicle comprising a composition as defined in the present description, said composition being simultaneously in contact with a first substrate and a second substrate of said vehicle, preferably in contact with a part of the bodywork of a vehicle and a window such as a windshield.

[0217] Furthermore, the present invention relates to the use of the composition according to the invention, as a sealant, in particular as a sealing joint.

[0218] Finally, the present invention relates to the use of the composition according to the invention, for bonding and sealing, in particular in the fields of building construction, transport, for example road, maritime, rail or aerospace, and shipbuilding, preferably in the field of road, maritime, rail or aerospace transport, in particular for fixing a window (for example a windshield or a window) to the bodywork of a vehicle, preferably for replacing the windshield of a vehicle.

[0219] All the embodiments described above may be combined with each other. In particular, the various aforementioned ingredients of the composition, and in particular the preferred embodiments of the composition, may be combined with each other.

[0220] The following examples are given purely for illustrative purposes of the invention and should not be interpreted as limiting its scope.

[0221] Examples

[0222] 1 Ingredients and measurement methods

[0223] Ingredients used

[0224] The following ingredients were used:

[0225] - MS POLYMER™ S303H marketed by KANEKA: poly(propylene oxide) with dimethoxysilane terminations with a number-average molar mass of 21 to 23 kg / mol, and a viscosity of 12.5 Pa.s;

[0226] - MS POLYMER™ SAX 725 marketed by KANEKA: poly(propylene oxide) with dimethoxysilane terminations with a mass-average molar mass Mw of approximately 51 kg / mol and a number-average molar mass of approximately 41 kg / mol, and a viscosity of 87 Pa.s;

[0227] - DYNASYLAN® VTMO marketed by EVONIK: vinyltrimethoxysilane (CAS No.: 2768-02-7), moisture absorber;

[0228] DYNASYLAN® AMMO marketed by EVONIK: (3-aminopropyl)trimethoxysilane (CAS No.: 13822-56-5), adhesion promoter;

[0229] - CALOFORT® SV14 marketed by Specialty Minerals: precipitated calcium carbonate coated with fatty acids, with an average particle size of 70 nm;

[0230] - OMYACARB 2T-AV marketed by OMYA: calcium carbonate (also called GCC for “Ground Calcium carbonate”) having a d50 particle size of 2.7 pm and a moisture content less than or equal to 0.2% relative to the total weight of OMYACARB 2T-AV;

[0231] - HAKUENKA® CCR-S10 marketed by OMYA: precipitated calcium carbonate coated with fatty acids, with an average particle size of 80 nm; - RIASORB UV-123 marketed by RIANLON: bis(1-octyloxy-2, 2,6,6-tetramethyl-4-piperidyl)sebacate (CAS No.: 129757-67-1), hindered amine light stabilizer (HALS);

[0232] - TINUVIN 770 DF marketed by BASF: bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate (CAS No.: 52829-07-9), hindered amine light stabilizer (HALS);

[0233] - PRINTEX® 25 marketed by Orion: carbon black with an OAN of 45 mL / 100 g measured according to the ASTM D-2414 method;

[0234] - ELFTEX® S5100 marketed by CABOT: carbon black with an OAN of 108 mL / 100 g measured according to the ASTM D-2414 method;

[0235] - ELFTEX® S7100 marketed by CABOT: carbon black having an OAN of 117 ± 6 mL / 100 g measured according to the ASTM D-2414 method;

[0236] - SILQUEST A-LINK 600 marketed by MOMENTIVE: 4-amino-3,3-dimethylbutyltrimethoxysilane (CAS No.: 157923-74-5), non-yellowing adhesion promoter;

[0237] - NEOSTANN S-1 marketed by KANEKA: silicic acid (H4SiO4), tetraethyl ester, reaction products with bis(acetyloxy)dibutylstannane (CAS No.: 93925-43-0), crosslinking catalyst;

[0238] - TIB KAT 425 marketed by TIB CHEMICALS: TIB KAT 232 mixture (dioctyltin oxide) / silane, crosslinking catalyst;

[0239] - THIXATROL® AS 8053 marketed by ELEMENTIS: micronized amide wax rheology agent with an average diameter of less than 5 pm;

[0240] - CRAYVALLAC® SLX marketed by ARKEMA: micronized amide wax rheology agent (particle size less than 5 pm);

[0241] - Hexamoll® DINCH marketed by BASF: diisononyl ester of 1,2-cyclohexanedicarboxylic acid, plasticizer.

[0242] Measurement methods

[0243] Tensile strength, elongation at break, modulus of elasticity and 100% modulus were measured in accordance with ISO 37 (December 2005), at a constant speed of 500 mm / min.

[0244] In particular, the following conditions were applied:

[0245] A standard dumbbell-shaped test piece, type 1, as illustrated in international standard ISO 37 (December 2005) is used. The narrow part of the dumbbell used has a length of 33 mm, a width of 6 mm and a thickness of 2 mm. To prepare the dumbbell, the composition to be tested is applied to a Teflon mold, and the composition is allowed to cure for 14 days under standard conditions (23°C and 50% relative humidity).

[0246] The principle of the measurement consists of stretching a standard test piece in a tensile machine, whose movable jaw moves at a constant speed equal to 500 mm / minute, and recording:

[0247] - the elongation at break (expressed in %) is the elongation of the specimen corresponding to the stretching observed at the time of break,

[0248] - the 100% modulus (in MPa) is the tensile stress corresponding to a 100% elongation of the specimen,

[0249] - the modulus of elasticity (expressed in MPa) is the slope of the tangent at the origin of the curve showing the tensile stress as a function of the elongation of the specimen, and

[0250] - tensile strength (in MPa) is the tensile stress at which the specimen ruptures.

[0251] The measurement is repeated for 5 test pieces, and the corresponding average of the results obtained is calculated.

[0252] Shear strength was measured using the following method:

[0253] Two rectangular aluminum plates measuring 100 mm x 25 mm x 2 mm are used. After cleaning the two plates with acetone, a rectangular bonding area measuring 12.5 mm x 25 mm is defined, using adhesive tape, at the end of each plate.

[0254] On the gluing area of ​​a 1 èresubstrate plate thus materialized, the silylated polymer composition is applied, in a quantity corresponding to a thickness of 2 mm. Then the bonding zone of the 2 is superimposed on the area thus coated ème substrate plate, so as to obtain an assembly in which the free ends of the 2 substrate plates are aligned on either side of the two areas joined by the mastic.

[0255] The assembly specimen obtained is held by clips for 14 days in a room with a controlled atmosphere at 23°C and 50% relative humidity, for crosslinking of the composition.

[0256] The two free ends of the specimen are pulled by means of a tensile machine at a constant speed equal to 50 mm / minute, until the assembly breaks, for which the applied stress is recorded. The measurement is repeated for 3 assembly specimens, and the average of the shear stresses at break (called shear strength) obtained is calculated.

[0257] It is also noted whether the rupture is cohesive (rupture within the composition) or adhesive (rupture at the composition / plate interface).

[0258] Example 2: Effect of carbon black incorporation as a function of its OAN

[0259] In a reactor maintained under stirring, the comparative composition 1a is prepared by mixing the ingredients in the proportions indicated in Table 1 Table 3 below, in several stages according to the process described below.

[0260] The ingredients in step 1 are mixed at room temperature (about 23°C), atmospheric pressure, and low stirring speed (enough to homogenize).

[0261] Then, the ingredients from step 2 are added to the reactor used for step 1, and mixed first at atmospheric pressure and high stirring speed (in order to shear and mix the solids), then the reactor is put under vacuum (16 kPa), the temperature is increased to 75-80°C and mixing is carried out for 10 to 30 min.

[0262] Finally, the ingredients from step 3 are added under vacuum and mixing is carried out at low stirring speed (enough to homogenize).

[0263] Table 1

[0264] Compositions 1b to 1e are prepared according to the same method as comparative composition 1a and have the same composition, except that:

[0265] - 2% by weight of CALOFORT SV14 are replaced by 2% by weight of PRINTEX 25, relative to the total weight of the composition, for comparative composition 1b; - 5% by weight of CALOFORT SV14 are replaced by 5% by weight of PRINTEX 25, relative to the total weight of the composition, for comparative composition 1c;

[0266] - 2% by weight of CALOFORT SV14 are replaced by 2% by weight of ELFTEX S5100, relative to the total weight of the composition, for composition 1 d according to the invention;

[0267] - 5% by weight of CALOFORT SV14 are replaced by 5% by weight of ELFTEX S5100, relative to the total weight of the composition, for composition 1 e according to the invention.

[0268] For example, comparative composition 1b has the same composition as 1a, except that it comprises 43.5% by weight of CALOFORT SV14 and 2% by weight of PRINTEX 25.

[0269] Carbon black (PRINTEX 25 or ELFTEX S5100) is also added during step 2 of the process.

[0270] The mechanical properties of compositions Nos. 1 to 4 (measured in accordance with Example 1) are summarized in Table 2 below.

[0271] Table 2

[0272] Comparison of the results obtained for compositions 1 a and 1 b allows us to conclude that the incorporation of PRINTEX 25 does not significantly increase the tensile strength of the composition, and allows a slight improvement in the elongation at break (increase of 11%).

[0273] Furthermore, when a larger amount of PRINTEX 25 is incorporated, this does not significantly increase the tensile strength of the composition, and has no influence on its elongation at break (comparison of the results obtained for compositions 1 b and 1 c). On the other hand, the tensile strength of composition 1d (2% ELFTEX S5100) is 21% higher than that of composition 1 a and its elongation at break has been improved by 28%, while the tensile strength of composition 1 e (5% ELFTEX S5100) is 38% higher than that of composition 1 a and its elongation at break has been improved by 22%.

[0274] Thus, the incorporation of ELFTEX S5100 (carbon black having an OAN of 108 mL / 100 g) into a silylated polymer composition makes it possible to significantly improve both the tensile strength and the elongation at break of the composition, this effect not being obtained with the incorporation of PRINTEX 25 (carbon black having an OAN of 45 mL / 100 g).

[0275] Example 3: comparative composition 2a not including a rheology agent

[0276] In a reactor maintained under stirring, the different ingredients of comparative composition 2a are mixed in the proportions indicated in Table 3 below, in several stages according to the following process.

[0277] The ingredients in step 1 are mixed at room temperature (about 23°C), atmospheric pressure, and low stirring speed (enough to homogenize).

[0278] Then, the ingredients from step 2 are added to the reactor used for step 1, and mixed first at atmospheric pressure and high stirring speed (in order to shear and mix the solids), then the reactor is put under vacuum (16 kPa), the temperature is increased to 75-80°C and mixing is carried out for 10 to 30 min.

[0279] Finally, the ingredients from step 3 are added under vacuum and the mixture is carried out at low stirring speed (enough to homogenize)

[0280] Table 3 Example 4: comparative composition 2b not including a rheology agent

[0281] Comparative composition 2b is similar to comparative composition 2a, except that a plasticizer has been added (Hexamoll® DINCH). In a stirred reactor, the various ingredients of comparative composition 2b are mixed in the proportions indicated in Table 4 below, in several stages, according to the method described in Example 3.

[0282] Table 4 Example 5: composition 2c according to the invention

[0283] Composition 2c according to the invention is similar to comparative composition 2b, except that a rheology agent has been added (THIXATROL® AS 8053).

[0284] In a reactor maintained under stirring, the different ingredients of composition 2c are mixed in the proportions indicated in Table 5 below, in several stages, according to the process described in Example 3 except that the temperature in stage 2 is increased to 50-55°C (corresponding to the activation temperature of THIXATROL® AS 8053) instead of 75-80°C.

[0285] Table 5

[0286] Example 6: 2d composition according to the invention

[0287] Composition 2d is similar to composition 2c, except that another rheology agent was used (CRAYVALLAC® SLX). In a stirred reactor, the different ingredients of composition 2d are mixed in the proportions indicated in Table 6 below, in several stages, according to the process described in Example 3.

[0288] Table 6 Example 7: mechanical properties of compositions 2a to 2d

[0289] The mechanical properties of compositions 2a to 2d (measured according to Example 1) are summarized in Table 7 below.

[0290] Table 7

[0291] The addition of a rheology agent in compositions 2c and 2d according to the invention makes it possible to significantly improve both the elongation at break and the tensile strength of the compositions. Indeed, in comparison with the comparative composition 2b which does not comprise a rheology agent, the tensile strength of composition 2c (THIXATROL® AS 8053) is 8% higher than that of composition 2b and its elongation at break has been improved by 23%, while the tensile strength of composition 2d (CRAYVALLAC® SLX) is 11% higher than that of composition 2b and its elongation at break has been improved by 25%.

[0292] Compositions 2c and 2d according to the invention also have the advantage of having a 100% cohesive fracture surface.

Claims

Demands 1. Composition comprising: a silylated polymer, - carbon black having an oil absorption rate (OAN) of at least 80 mL / 100 g, and - a rheology agent.

2. Composition according to claim 1, wherein the silylated polymer comprises at least one, preferably at least two, alkoxysilane groups of formula (I): ~If(R 4 ) P (OR5)^ (I) in which: - R 4 represents a linear or branched alkyl radical comprising 1 to 4 carbon atoms, and when p equals 2, the R radicals 4 are identical or different, - R 5 represents a linear or branched alkyl radical comprising 1 to 4 carbon atoms, and when p is equal to 0 or 1, the R radicals 5 are identical or different, two OR groups 5 that can be engaged in the same cycle, and - p is an integer equal to 0, 1 or 2, preferably equal to 0 or 1.

3. Composition according to claim 1 or 2, wherein the silylated polymer is of formula (II), (III) or (IV): in which: - R 4 , R 5 and p have the same meaning as in formula (I) described above, - P represents a saturated or unsaturated polymeric radical, with a linear or branched open chain, or comprising one or more rings, possibly aromatic, possibly comprising one or more heteroatoms, such as oxygen, nitrogen, sulfur and / or silicon, preferably oxygen and / or nitrogen, and possibly comprising one or more ionic groups, - R 1 represents a divalent hydrocarbon radical comprising 5 to 15 carbon atoms, saturated or unsaturated, with a linear or branched open chain, or comprising one or more possibly aromatic rings, R3 represents a linear or branched alkylene divalent radical comprising 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, - X represents a divalent radical chosen from -NH-, -NR 7 - or -S-, - R 7 represents a linear or branched alkyl radical comprising from 1 to 20 carbon atoms and possibly also comprising one or more heteroatoms, - f is an integer from 1 to 6, advantageously from 2 to 5, preferentially from 2 to 4, even more preferably from 2 to 3.

4. Composition according to claim 3, wherein the silylated polymer is of formula (IT), (II”), (III') or (IV): (R 5 O) 3.p (R 4 ) p If— R 3 — O- 0- R 2 £p- R 3 - If(R 4 ) p (GOLD 5 ) 3.p (HI') in which: R 1 , R3 , R 4 , R 5 , X, R 7 and p have the same meaning as in formulas (II), (III) and (IV), - R 2 represents a saturated or unsaturated, linear or branched, divalent hydrocarbon radical, possibly comprising one or more heteroatoms, such as oxygen, nitrogen, sulfur, silicon, and possibly comprising one or more ionic groups, - n is an integer, preferably n is such that the number-average molar mass of the silylated polymer is between 500 g / mol and 70000 g / mol, more preferably between 4000 g / mol and 60000 g / mol, even more preferably between 10000 g / mol and 50000 g / mol.

5. Composition according to claim 4, wherein the silylated polymer is a polymer of formula (III') and wherein: - R 2 represents an isopropylene radical, - R 4 and R 5 each represent a methyl radical, and - p is equal to 1.

6. Composition according to any one of claims 1 to 5, wherein the carbon black content is at least 2% by weight relative to the total weight of the composition, preferably from 3% to 20% by weight, more preferably from 5% to 18% by weight, even more preferably from 6% to 15% by weight, for example 6%.

7. Composition according to any one of claims 1 to 6, wherein the rheology agent is one or more thixotropic agents.

8. Composition according to any one of claims 1 to 7, wherein the rheology agent is an amide wax and / or a wax derived from castor oil, preferably an amide wax.

9. Composition according to any one of claims 1 to 8, further comprising at least one adhesion promoter selected from amino-, mercapto- and epoxy-alkoxysilanes, preferably selected from aminoalkoxysilanes, more preferably from aminotrimethoxysilanes, and even more preferably from aminotrimethoxysilanes.

10. Composition according to claim 9, wherein the at least one adhesion promoter is a mixture of at least two adhesion promoters, preferably of two adhesion promoters.

11. Composition according to claim 10, wherein at least one adhesion promoter is a mixture of two adhesion promoters selected from 4-amino-3,3-dimethylbutyltrimethoxysilane, (3-aminopropyl)trimethoxysilane and n-butyl-3-aminopropyl-trimethoxysilane.

12. A method for joining two substrates by bonding, comprising: - coating, on at least one of the two substrates to be assembled, with the composition according to any one of claims 1 to 11; then - the effective contacting of the two substrates.

13. Use of the composition according to any one of claims 1 to 11, as a sealant, in particular as a sealing gasket.

14. Use of the composition according to any one of claims 1 to 11, for bonding and sealing in particular in the fields of building construction, transport, for example road, sea, rail or aerospace, and shipbuilding, preferably in the field of road, sea, rail or aerospace transport, in particular for fixing a piece of glass (for example a windscreen or window) to the body of a vehicle, preferably for replacing the windscreen of a vehicle.

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