Composition comprising a silylated polymer

Abstract

The invention relates to a composition comprising: a silylated polymer, carbon black having an oil absorption rate (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 bonding and sealing. Figure for the abstract: none

Description

Title of the invention: Composition comprising a silylated polymer Scope of the invention

[0001] The present invention relates to a composition comprising a silylated polymer, and its use in particular for bonding and sealing. Technical background

[0002] Various polymer-based compositions are available on the market, which can be used in numerous fields, particularly as sealants. Sealants allow for the assembly (or joining or bonding) of two substrates, which can be chosen from a wide variety of materials, and can also be used as seals. Sealants provide the resulting assembly with advantageous mechanical properties of strength, elasticity and / or flexibility, as well as fluid tightness.

[0003] For example, polymer-based compositions can be used as sealants in building construction, shipbuilding, or the transport sector (e.g., road, sea, rail or aerospace).

[0004] Certain applications, particularly the attachment of glass (for example, a windshield or window) to a vehicle body, require that the polymer-based composition have specific mechanical properties, especially high tensile strength and high elongation at break. Indeed, it is essential that the composition not break under impact.

[0005] Compositions on the market for windshield replacement are usually polyurethane-based compositions with isocyanate terminations, which generally exhibit high tensile strength and high elongation at break. During the application of the composition for assembly, the reaction of the reactive isocyanate groups with water from atmospheric humidity and / or the substrates to be bonded is called the crosslinking reaction. It is the completion of this reaction, after a period known as the 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.

[0006] Compositions based on alkoxysilane-terminated polymers (also called silylated polymers) have the advantage of being isocyanate-free. These compositions therefore constitute a toxicologically preferred alternative to isocyanate-terminated polyurethane compositions.

[0007] The crosslinking reaction of these silylated polymer-based compositions occurs, in the presence of moisture, through 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.

[0008] However, it is difficult to obtain a composition, particularly a sealant, based on silylated polymer that has 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 isocyanate-terminated polyurethane.

[0009] There is therefore a need to find a composition comprising a silylated polymer having improved tensile strength and elongation at break properties, in particular approaching isocyanate-terminated polyurethane-based compositions. Summary of the invention

[0010] The present invention relates to a composition comprising:

[0011] - a silylated polymer, - carbon black having an oil absorption rate (OAN) of at least 80 mL / 100 g, and - a rheology agent.

[0012] The present invention also relates to a method for assembling two substrates by bonding, comprising:

[0013] - the coating, on at least one of the two substrates to be assembled, of the composition according to the invention, as defined above; then

[0014] - the effective contacting of the two substrates.

[0015] The present invention also relates to an article that can be obtained according to the assembly process as defined above, preferably a vehicle.

[0016] The present invention also relates to a vehicle comprising a composition as defined in this description, said composition being simultaneously in contact with a first substrate and a second substrate of said vehicle.

[0017] Furthermore, the present invention relates to the use of the composition according to the invention, as a sealant, in particular as a sealing gasket.

[0018] Finally, the present invention relates to the use of the composition according to the invention, for bonding and sealing.

[0019] Surprisingly, it has been found that adding a combination of a rheology agent and carbon black having a high OAN to a silylated polymer composition significantly improves both the tensile strength and elongation at break properties of the composition.

[0020] The composition according to the invention is therefore particularly advantageous for fixing a pane of glass (for example a windshield or a window) to the body of a vehicle, particularly for replacing a vehicle's windshield. Description of the invention

[0021] Thus, the invention relates to a composition comprising:

[0022] - a silylated polymer, - carbon black having an oil absorption rate (OAN) of at least 80 mL / 100 g, and - a rheology agent. Silyl polymer

[0023] The term "silylated polymer" means a polymer comprising at least one alkoxysilane group. Preferably, the silylated polymer comprises at least one alkoxysilane group at the polymer's termination.

[0024] 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.

[0025] The viscosity of the silylated polymer can for example be measured according to a Brookfield type method at 23°C and 50% relative humidity (needle S28).

[0026] In the context 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%.

[0027] Advantageously, the silylated polymer comprises at least one, preferably at least two, alkoxysilane groups of formula (I):

[0028] -Si(R4)p(OR5)3.p (I)

[0029] in which:

[0030] - R4 represents a linear or branched alkyl radical comprising 1 to 4 carbon atoms, and when p is equal to 2, the R4 radicals are either identical or different, - R5 represents a linear or branched alkyl radical comprising 1 to 4 carbon atoms, and when p is equal to 0 or 1, the R5 radicals are identical or different, two OR5 groups being able to be involved in the same ring, and - p is an integer equal to 0, 1 or 2, preferably equal to 0 or 1.

[0031] Preferably, the alkoxysilane groups of the silylated polymer have formula (I) with:

[0032] - R4 and R5 each represent a methyl radical, and - p is equal to 0 or 1.

[0033] Advantageously, the silylated polymer has an average molar mass in number between 500 g / mol and 70000 g / mol, preferably between 4000 g / mol and 60000 g / mol, more preferably between 10000 g / mol and 50000 g / mol.

[0034]

[0035]

[0036] The molar mass of polymers can be measured by well-known methods of a person skilled in the art, for example by NMR or size exclusion chromatography steric using polystyrene-type standards. Advantageously, the silylated polymer has formula (II), (III) or (IV): in which: -P -f year p -O--R: (no NH-R—

[0037]

[0038] (IV) - R4, R5 and p have the same meaning as in formula (I) described above, - P represents a saturated or unsaturated, open-chain polymeric radical linear or branched, 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, - R1 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-, -NR7- or -S-, - R7 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. Advantageously, the silylated polymer is of formula (II), (III) or (IV) with P representing a polymer radical selected from polyethers, polycarbonates, polyesters, polyolefins, polyacrylates, polyether polyurethanes, polyester polyurethanes, polyolefin polyurethanes, polyacrylate polyurethanes, polycarbonate polyurethanes, polyether / polyester block polyurethanes and polysiloxanes, preferably selected among polyethers, polyurethanes and their mixtures, more preferentially among polyethers.

[0039] Preferably, the silylated polymer has the formula (II'), (II”), (III') or (IV'):

[0040] R?l-O—C—O—RH-O—6—NH-R^Si<-R4UORX_ h t|| |.| i || - ,-p C< O 0 '■ O

[0041]

[0042]

[0043]

[0044]

[0045] (II’) (R%) vp(R %Si-~ R3- O NH-R^SKR^OR5)^ (II”) (R^kJlÔSvSï-RS^ r4o- R”MKR4UOR5Hn ' '' " n ’ ■ r (IID

[0046] s . s : r ; -, , . : ; (R O^^R kS—R—X—0—RH-R—NH-C—G—R-ko—O—NH-R—MH-C—G—rU-O—C—NH-R—X—R—SiïR ^OR \ . P II II L || H Jn H || ’ *• G G O Q ” G G

[0047] (IV')

[0048] in which:

[0049] - R1, R3, R4, R5, X, R7 and p have the same meaning as in formulas (II), (III) and (IV), - R2 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.

[0050] In the silylated polymers of formulas (II'), (II”), (III'), or (IV') defined above, when the radical R2 comprises one or more heteroatoms, said heteroatom(s) are not located at the end of the chain. In other words, the free valences of the divalent radical R2, bonded to the neighboring oxygen atoms of the silylated polymer, each originate from a carbon atom. Thus, the main chain of the radical R2 terminates with a carbon atom at each of its two ends, said carbon atom then exhibiting a free valence.

[0051] According to one embodiment, the silylated polymers are obtained from polyols selected from polyether polyols, polyester polyols, polycarbonate polyols, polyacrylate polyols, polysiloxane polyols, polyolefin polyols and mixtures thereof, preferably from diols selected from polyether diols, polyolefin polyols and mixtures thereof, preferably from diols selected from polyether diols, polyolefin polyols and mixtures thereof, preferably from diols selected from polyether diols, polyolefin polyols and mixtures thereof. Lyester diols, polycarbonate diols, polyacrylate diols, polysiloxane diols, polyolefin diols and their mixtures, more preferably among the polyether diols. In the case of polymers of formulas (II'), (II”), (III') or (IV') described above, such diols can be represented by the formula HO-R2-OH or H-[O-R2]n-OH, where R2 has the same meaning as in formulas (II'), (II”), (III') or (IV').

[0052] In particular, in the silylated polymer of formula (IV') defined above, the radical R 2 can be identical or different, that is to say that the silylated polymer of formula (IV') can be a silylated copolyurethane obtained from identical or different HO-R2-OH diols.

[0053] According to one embodiment, when the silylated polymer has formula (II') or (IV'), the radical R2 can be chosen from the following divalent radicals whose formulas below show the two free valences:

[0054] \ F CH'j CHa Ct

[0055] - derivative of a polyester diol: O

[0056] î* L

[0057] - derivative of a polybutadiene diol:

[0058] „ KQ' Q —qÏc—cTq— F°. 0 Q

[0059] - derivative of a polyacrylate diol:

[0060] Q Q5 Q' —Q—Si - O-FsiÔl—Si—Q— U l6"WQQQ

[0061] - derivative of a polysiloxane diol:

[0062] in which: - derivative of a polypropylene glycol: l Â Ï ,1 Q2 Q o' v (F Jq

[0063] - q represents an integer such that the number-molar mass of the radical R2 ranges from 100 g / mol to 48600 g / mol, preferably from 300 g / mol to 18600 g / mol, preferably again from 500 g / mol to 12600 g / mol,

[0064] - r and s represent zero or a non-zero integer such that the average molar mass in the number of radical R2 ranges from 100 g / mol to 48600 g / mol, preferably from 300 g / mol to 18600 g / mol, preferably again from 500 g / mol to 12600 g / mol, it being understood that the sum r+s is not zero,

[0065] - Q1 represents a linear aromatic or aliphatic divalent alkylene radical or branched, saturated or unsaturated, preferably having from 1 to 18 carbon atoms, preferably from 1 to 8 carbon atoms,

[0066] - Q2 represents a linear or branched divalent alkylene radical exhibiting preferably from 2 to 36 carbon atoms, preferably from 1 to 8 carbon atoms,

[0067] - Q3, Q4, Q5, Q6, Q7 and Q8, represent, independently of each other, an atom hydrogen or an alkyl, alkenyl or aromatic radical, preferably having 1 to 12 carbon atoms, preferably 2 to 12 carbon atoms, preferably still 2 to 8 carbon atoms.

[0068] According to a particular embodiment, when the silylated polymer has formula (IV'), the silylated polymer can be obtained from different HO-R2-OH diols, in which a radical R2 can 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 R2 is the ionic divalent radical of formula:

[0069] R^ ---(CHj)*---(CHgly---

[0070] in which:

[0071] - x and y, whether identical or different, are integers ranging from 1 to 8,

[0072] - z is an integer ranging from 0 to 8,

[0073] - R° represents a hydrogen atom or an alkyl radical comprising from 1 to 18 carbon atoms, and

[0074] - R, R' and R", identical or different, each represent a hydrocarbon radical saturated, unsaturated, or aromatic, possibly comprising a heteroatom selected from N, O, and S; R, R', and R" further being such that the tertiary amine of formula N(R)(R')(R") is a linear, branched, or cyclic amine or polyamine with a number-average molar mass (Mn) ranging from 59 to 6000 g / mol and exhibiting a pKa greater than 8.

[0075] According to one embodiment, R1 is chosen from the following divalent radicals whose formulas below show the two free valences:

[0076] a. the divalent radical derived from isophorone diisocyanate (IPDI):

[0077] CH3-'x

[0078] a. the divalent radical derived from dicyclohexylmethane diisocyanate (H12MDI):

[0079] / \ / \

[0080] c) divalent radicals derived from the 2,4- and 2,6- isomers of toluene diisocyanate (TDI):

[0081]

[0082] d) divalent radicals derived from the 4,4' and 2,4'- isomers of diphenylmethane di socyanate (MDI):

[0083]

[0084] e) the divalent radical derived from hexamethylene diisocyanate (HDI): -(CH2)6-

[0085] f) the divalent radical derived from m-xylylene diisocyanate (m-XDI):

[0086] According to a preferred embodiment, the silylated polymer is of formula (II”) or (III'), preferably (III'), and the radical R2 preferably represents a linear or branched alkylene divalent radical comprising 2 to 4 carbon atoms, more preferably a linear or branched alkylene divalent radical comprising 3 carbon atoms, even more preferably an isopropylene radical (of formula -CH2 -CH(CH3)-).

[0087] According to a particularly preferred embodiment, the silylated polymer is a polymer of formula (III') in which:

[0088] - R2 represents an isopropylene radical, - R4 and R5 each represent a methyl radical, and - p is equal to 1.

[0089] Polymers of formula (II), (II') or (II”) can be obtained by a process described, for example, in documents EP 2336208 and WO 2009 / 106699. Examples of polymers conforming to formula (II) include:

[0090] - GENIOSIL® STP-E10 (available from WACKER-CHEMIE): polyether of formula (II”) comprising two groups of formula (I) of dimethoxy type (p equal to 1 and R4 and R5 represent a methyl group) having a number-average molar mass of 8889 g / mol where R3 represents a methyl group; GENIOSIL® STP-E30 (available from WACKER-CHEMIE): polyether of formula (II”) comprising two groups of formula (I) of dimethoxy type (p equal to 1 and R4 and R5 represent a methyl group) having a number-average molar mass of 14493 g / mol where R3 represents a methyl group; - DESMOSEAL® S XP 2636 (available from BAYER): polyurethane comprising two formula (I) groups of the trimethoxy type (p equals 0 and R5 represents a methyl group) having a number-average molar mass of 15038 g / mol where R3 represents an n-propylene group.

[0091] Polymers of formula (III) or (III') can be obtained by hydrosilylation of polyether diallylether according to a process described, for example, in document EP 1829928. Among the polymers corresponding to formula (III), the following may be mentioned:

[0092] - the MS SAX® 350 polymer (available from KANEKA) corresponding to a polyether comprising two formula (I) groups of dimethoxy type (p equal to 1 and R4 and R5 represent a methyl group) having a number-average molar mass ranging from 14000 to 16000 g / mol;

[0093] - the MS SAX® 260 polymer (available from KANEKA) corresponding to a polyether comprising two formula (I) groups of dimethoxy type (p equal to 1, R4 and R5 represent a methyl group) having a number average molar mass of 16000 to 18000 g / mol where R3 represents an ethyl group;

[0094] - the MS S303H polymer (available from KANEKA) corresponding to a polyether comprising two formula (I) groups of dimethoxy type (p is equal to 1 and R4 represents a methyl group) having a number average molar mass of 21000 to 23000 g / mol;

[0095] - the MS SAX® 725 polymer (available from KANEKA) corresponding to a polyether (R2 represents an isopropylene radical) comprising two groups of formula (I) of the dimethoxy type (p is equal to 1, R4 and R5 represent a group methyl) having a number-average molar mass of approximately 41 kg / mol.

[0096] Polymers of formula (IV) or (IV') can, for example, be obtained by reacting polyol(s) with one or more diisocyanates 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. Those skilled in the art will be able to adapt the manufacturing process described in this document when using different types of polyols. Examples of polymers corresponding to formula (IV) include:

[0097] - SPUR+® 1050MM (available from MOMENTIVE): polyurethane comprising two formula (I) groups of the trimethoxy type (p equals 0 and R5 represents a methyl group) having a number-average molar mass of 16393 g / mol where R3 represents an n-propyl group; - SPUR+® Y-19116 (available from MOMENTIVE): polyurethane comprising two groups of formula (I) of the trimethoxy type (p equal to 0 and R5 represents a methyl group) having an average number molar mass ranging from 15000 to 17000 g / mol g / mol where R3 represents an n-propyl group.

[0098] The silylated polymer content in the composition according to the invention can 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, and even more preferably from 30% to 45% by weight, particularly from 35% to 40% by weight. Carbon black

[0099] The carbon black in the composition according to the invention has an oil absorption index (OAN) of at least 80 mL / 100 g.

[0100] The OAN of a carbon black corresponds to the volume in mL of dibutyl phthalate oil (DBP) absorbed by 100 g of carbon black

[0101] The OAN can for example be measured according to the ASTM D-2414 method and using DBP oil.

[0102] Unless otherwise indicated, the standards referred to throughout the application are those in force at the date of filing of the application.

[0103] The carbon black implemented 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.

[0104] Indeed, the carbon blacks used as pigments are of lower quality and have a lower OAN than the carbon black implemented in the present invention.

[0105] An example of carbon black used as a pigment is PRINTEX® 25 (marketed by Orion), which has an OAN of 45 mL / 100 g.

[0106] Examples of carbon black that can be implemented in the present The inventions are ELFTEX® S7100 and ELFTEX® S5100 (marketed by CABOT), having respectively an OAN of approximately 117 and 108 mL / 100 g.

[0107] By "approximately X", we mean plus or minus 10% of the value of X.

[0108] Preferably, the OAN of 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.

[0109] 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 from 6%. Rheology agent

[0110] The rheology agent allows the rheological properties of the composition according to the invention to be adjusted.

[0111] By way of example, one can cite any rheology agent commonly used in the field of mastic compositions.

[0112] Advantageously, one or more rheological agents are used, selected from:

[0113] - PVC plastisols, corresponding to a suspension of PVC in an agent plasticizer miscible with PVC, obtained in situ by heating to temperatures ranging from 60°C to 80°C. These plastisols may be those described in particular in the book "Polyurethane Sealants", Robert M. Evans, ISBN 087762-998-6;

[0114] - fumed silica, such as HDK® N20 marketed by WACKER;

[0115] - urea derivatives resulting from the reaction of an aromatic diisocyanate monomer such that 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;

[0116] - waxes derived from castor oil, such as THIXCIN® R available from ELEMENTIS,

[0117] - 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.

[0118] By "waxes derived from castor oil" means waxes obtained from castor oil, in particular from hydrogenated castor oil.

[0119] 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) (for example ricinoleic acid) and (di)amine(s).

[0120] Preferably, the rheology agent is an amide wax and / or oil derivative of castor oil, more preferably an amide wax.

[0121] The amide waxes are preferably micronized, that is to say, they have a particle size of less than 1 mm. Advantageously, the amide waxes have a particle size of less than 500 pm, preferably less than 100 pm, more preferably less than 10 pm.

[0122] The average particle size advantageously corresponds 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).

[0123] Wax-amide type rheology agents can be heat-activated, i.e. a temperature above ambient temperature (23°C) may be required to activate it during the preparation of the composition according to the invention.

[0124] The activation temperature depends on the rheology agent.

[0125] For example, THIXATROL® AS8053 is generally activated at a temperature between 50°C and 55°C, and CRAYVALLAC® SLX is generally activated at a temperature between 75°C and 80°C.

[0126] Advantageously, the content of the 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. Adhesion promoter

[0127] The composition according to the invention may further comprise at least one adhesion promoter.

[0128] Advantageously, the adhesion promoter is chosen from among amino-, mercapto- and epoxy-alkoxysilanes, preferably chosen from among aminoalkoxysilanes, more preferably from among aminotrialkoxysilanes, even more preferably, from among aminotrimethoxysilanes.

[0129] As an example of an epoxy-alkoxysilane, we can cite (3-Glycidyloxypropyl)trimethoxysilane (also called GLYMO).

[0130] Advantageously, 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, aminotrimethoxysilanes are formed by the group consisting of 4-amino-3,3-dimethylbutyltrimethoxysilane and (3-aminopropyl)trimethoxysilane.

[0131] Advantageously, the composition according to the invention comprises at least one adhesion promoter.

[0132] According to a preferred embodiment, the at least one adhesion promoter is a mixture of at least two adhesion promoters, preferably of two adhesion promoters.

[0133] According to this preferred embodiment, the adhesion promoters are selected from aminoalkoxysilanes, preferably from aminotrimethoxysilanes, and more preferably from aminotrimethoxysilanes. Preferably, the adhesion promoter is a mixture of two adhesion promoters selected from 4-amino-3,3-dimethylbutyltrimethoxysilane, (3-aminopropyl)trimethoxysilane, and n-butyl-3-aminopropyltrimethoxysilane. More preferably, the adhesion promoter is a mixture of 4-amino-3,3-dimethylbutyltrimethoxysilane and (3-aminopropyl)trimethoxysilane.

[0134] According to a preferred embodiment in which the adhesion promoter is a mixture of two adhesion promoters, the weight ratio (1st adhesion promoter) / (2nd 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.

[0135] 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.

[0136] Advantageously, the composition according to the invention further comprises a filler.

[0137] Preferably, the filler is chosen from mineral fillers, organic fillers and their mixtures, more preferably from mineral fillers.

[0138] Advantageously, the mineral fillers are formed by the group consisting of clay, quartz, hollow mineral microspheres and carbonate fillers.

[0139] Among hollow mineral microspheres, we can mention hollow glass microspheres, and more particularly those made of sodium and calcium borosilicate or of alu-minosilicate.

[0140] Preferably, the mineral fillers are formed by the group consisting of carbonate fillers.

[0141] According to a preferred embodiment, the composition according to the invention further comprises a carbonate filler, advantageously the carbonate filler is chosen from alkali or alkaline-earth metal carbonates and their mixtures, preferably the carbonate filler comprises calcium carbonate, more preferably the carbonate filler is chalk or calcium carbonate coated with fatty acids, even more preferably precipitated calcium carbonate coated with fatty acids.

[0142] When calcium carbonate is coated with fatty acids, this makes it possible to impart total or partial hydrophobicity to the calcium carbonate particles. Furthermore, The fatty acid coating acts as a hydrophobic coating that can prevent the calcium carbonate from absorbing the other components of the composition and rendering them ineffective. This hydrophobic coating of calcium carbonate can represent from 0.1% to 3.5% by weight, relative to the total weight of calcium carbonate.

[0143] Preferably, the fatty acids coating the calcium carbonate comprise or consist of more than 50% by weight of stearic acid relative to the total weight of fatty acids.

[0144] As an example of non-precipitated fatty acid coated calcium carbonate, we can cite OMYACARB 2T-AV or OMYA BLH (marketed by OMYA), or CALATEM C16T (marketed by Provençale).

[0145] Examples of precipitated calcium carbonate coated with fatty acids include HAKUENKA® CCR-S10 (marketed by OMYA) or CALOFORT® (marketed by Specialty Minerals).

[0146] 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.

[0147] Advantageously, the average particle size of the charge 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.

[0148] The average particle size advantageously corresponds 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).

[0149] 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. Crosslinking catalyst

[0150] The composition according to the invention may further comprise a crosslinking catalyst.

[0151] The crosslinking catalyst may be any catalyst known to those skilled in the art for the condensation of silanol. Examples of such catalysts include:

[0152] - organic derivatives of titanium such as titanium acetyl acetonate (for example the TYZOR® AA75 marketed by Dorf Ketal),

[0153] - of aluminium such as aluminium chelate (for example K-KAT® 5218 com (marketed by KING INDUSTRIES),

[0154] - amines such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or the 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), diethyl ether-2,2'-morpholine (DMDEE), 1,4-diazabicyclo[2.2.2]octane (DABCO),

[0155] - zinc carboxylate and DBU-based catalysts (for example K-KAT® 670 marketed by KING INDUSTRIES),

[0156] - tin-based catalysts such as compounds derived from dioctyltin or di- Butyltin; in particular dioctyltin oxide, dioctyltin diacetate, dioctyl tin dilaurate, dioctyl tin dicarboxylate, dibutyl tin diacetate (DBTDAA), dibutyl tin dilaurate (DBTDL), dibutyl tin diacetate, or dibutyl tin oxide, preferably dioctyl tin or dibutyl tin oxide. Examples include NEOSTANN® Sl (marketed by KANEKA), or TIB KAT® 425 or TIB KAT® 423 (marketed by TIB CHEMICALS).

[0157] - guanidine derivatives such as l-(o-tolyl)biguanide (CAS No.: 93-69-6), by example RHENOCURE 1000 C (marketed by RheinChemie Additives).

[0158] Preferably, the crosslinking catalyst is a tin-based catalyst, preferably selected from compounds derived from dioctyltin and dibutyltin, more preferably from dioctyltin or dibutyltin oxide.

[0159] The content of crosslinking catalyst in the composition according to the invention can 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.

[0160] 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, that is to say, an organic compound derived from silicic acid comprising at least two alkoxysilane groups. Examples include tetraethoxysilane (e.g., WACKER® TES 28 or TES 40 WN) or 1,2-bis(triethoxysilyl)ethane (e.g., Dynasylan® BTSE).

[0161] The content of the 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. Other additives

[0162] The composition according to the invention may further comprise at least one additive selected from plasticizers, moisture absorbers, solvents, UV stabilizers and mixtures thereof.

[0163] Advantageously, the composition according to the invention comprises a mixture of additives selected from plasticizers, moisture absorbers, solvents and UV stabilizers (or antioxidants).

[0164] The total content of additives in the composition according to the invention can range from 0.5% at 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.

[0165] Advantageously, the composition according to the invention comprises a plasticizer.

[0166] The plasticizer can be any plasticizer commonly used in the field of sealant compositions.

[0167] Preferably, the plasticizer is chosen from:

[0168] - diisodecyl phthalate (for example PALATINOL® DIDP marketed by BASF),

[0169] - diisononyl phthalate (DINP) (for example PALATINOL® N marketed by BASF),

[0170] - an ester of alkylsulfonic acid and phenol (for example MESAMOLL® marketed by LANXESS),

[0171] - the diisononyl ester of 1,2-cyclohexanedicarboxylic acid (for example the HEXAMOLL DINCH® (marketed by BASF), and

[0172] - pentaerythritol tetravalerate (for example PEVALEN™ marketed by PERSTORP).

[0173] More preferably, the plasticizer is the diisononyl ester of acid 1,2-cyclohexanedicarboxylic acid.

[0174] 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.

[0175] 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 volatile at room temperature (approximately 23°C). The volatile solvent may, for example, be chosen from alcohols 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 it easier to apply. The volatile nature of the solvent allows the joint, obtained after the composition has hardened, to no longer contain any solvent. Thus, the solvent does not, for example, have a negative influence on the hardness of the joint.

[0176] 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 can be selected from vinyltrimethoxysilane (for example, DYNASYLAN® VTMO marketed by EVONIK), propyltrimethoxysilane (for example, DYNASYLAN® PTMO marketed by EVONIK), vinyltriethoxysilane (VTEO), alkoxy-arylsilanes (for example, GENIOSIL® XL 70 marketed by WACKER), p-toluenesulfonyl isocyanate (PTSI) and calcium oxide.

[0177] Preferably, the moisture absorber is chosen from vinyltrimethoxysilane, the vinyltriethoxysilane and alkoxyarylsilanes, more preferentially vinyltrimethoxysilane.

[0178] 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. The UV stabilizers are typically introduced to protect the composition from degradation resulting from a reaction with oxygen that may be formed by the action of heat or light. These compounds may include antioxidants capable of scavenging free radicals.

[0179] Advantageously, the UV stabilizer(s) (or antioxidant(s)) are selected from among benzotriazoles, benzophenones, so-called hindered amines such as bis(l-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(l,2,2,6,6-pentamethyl-4-piperidyl)sebacate (CAS No. 41556-26-7), methyl l,2,2,6,6-pentamethyl-4-piperidyl sebacate (CAS No. 82919-37-7), octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, the 4,4'-bis(a,a-dimethylbenzyl)diphenylamine, and their mixtures. Examples include IRGANOX 1076, TINUVIN® 292, TINUVIN® 765 or TINUVIN® 770 DF marketed by BASF, RIASORB UV-123 marketed by RIANLON, AddWorks® IBC 760 marketed by CLARIANT and OKABEST CLX 50 marketed by OKA.

[0180] Preferably, the UV stabilizer(s) (or antioxidants) are chosen from among so-called hindered amines such as bis(l-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.

[0181] More preferably, the UV stabilizers (or antioxidants) are a mixture of bis(l-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)octadecyl propionate and 4,4'-bis(a,a-dimethylbenzyl)diphenylamine.

[0182] Other characteristics of the composition according to the invention

[0183] According to one embodiment, the composition according to the invention comprises:

[0184] - from 5% to 60% by weight of silylated polymer, relative to the total weight of the composition, - 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, - from 0.2% to 20% by weight of rheological agent, relative to the total weight of the composition, - 0.2% to 5% by weight of adhesion promoter(s), relative to the total weight of the composition, - from 10% to 80% by weight of the filler, relative to the total weight of the composition, - from 0.01% to 5% by weight of crosslinking catalyst, relative to the total weight of the composition, - optionally from 0.01% to 5% by weight of crosslinking cocatalyst relative to the total weight of the composition, and - 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.

[0185] Preferably, the composition according to the invention consists essentially of the ingredients mentioned above. By "consists essentially of" means 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, and even more preferably less than 1% by weight.

[0186] The ingredients of this embodiment and their particular contents are as described above, including the embodiments.

[0187] According to a particular embodiment, the composition according to the invention comprises:

[0188] - 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 (in'), - 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, - 1% to 5% by weight of rheological agent, relative to the total weight of the composition, the rheological agent being an amide wax, - 1.0% to 2.0% by weight of adhesion promoters, relative to the total weight of the composition, the adhesion promoters being chosen from among the ami-no-trimethoxy silanes, - 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, - 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, - optionally 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 - 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.

[0189] Preferably, the composition according to the invention consists essentially of the ingredients mentioned above.

[0190] The ingredients of this embodiment and their particular contents are as described above, including the embodiments.

[0191] 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.

[0192] 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%.

[0193] 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%.

[0194] A person skilled in the art 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.

[0195] In particular, tensile strength and elongation at break can be measured as described in Example 1 below. Preparation of the composition according to the invention

[0196] The composition according to the invention can be prepared by simply mixing its ingredients.

[0197] According to a preferred embodiment, the composition according to the invention is prepared according to the following process:

[0198] - 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 - 2) Carbon black having an OAN of at least 80 mL / 100 g, and any Other solid ingredients such as rheology agent, filler, and solid additives like a UV stabilizer (or antioxidant) are dispersed in the previous liquid mixture for the time necessary to obtain a homogeneous mixture, then - 3) the remaining liquid ingredients, such as promoter Adhesion agent and catalyst are added and the medium is homogenized.

[0199] Preferably, step 2) is carried out at a pressure lower than atmospheric pressure, more preferably at a pressure lower than 50 kPa, even more preferably at a pressure lower than 20 kPa.

[0200] Preferably, step 2) is carried out at a temperature above 30°C, more preferably above 40°C. When the composition according to the invention includes a heat-activated rheology agent, the mixing of the solid ingredients is advantageously carried out at a temperature at which the rheology agent is activated.

[0201] Preferably, step 3) is carried out at a pressure and temperature approximately equal to those carried out in step 2).

[0202] An example of preparing the composition according to the invention is described in Example 2. Other objects of the present invention

[0203] The present invention also relates to a method for assembling two substrates by bonding, comprising:

[0204] - coating, on at least one of the two substrates to be assembled, with the composition according to the invention, as defined above; then

[0205] - the effective contacting of the two substrates.

[0206] The substrates concerned are very varied, and preferably chosen from concrete, a metal such as aluminium and / or steel and glass.

[0207] According to a preferred embodiment, one of the substrates is steel (for example, part of the body of a vehicle) and the other substrate is glass (for example, a pane of glass such as a windshield or window).

[0208] The present invention also relates to an article that can be obtained according to the assembly process as defined above, preferably a vehicle.

[0209] The present invention also relates to a vehicle comprising a composition as defined in this 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 a vehicle's bodywork and a piece of glass such as a windshield.

[0210] Furthermore, the present invention relates to the use of the composition according to the invention, as a sealant, in particular as a sealing gasket.

[0211] Finally, the present invention relates to the use of the composition according to the invention, for bonding and sealing particularly 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, particularly for fixing a glass (for example a windscreen or a window) to the body of a vehicle, preferably for replacing the windscreen of a vehicle.

[0212] All the embodiments described above can be combined with each other. In particular, the various aforementioned ingredients of the composition, and especially the preferred embodiments, can be combined with each other.

[0213] The following examples are given purely for illustrative purposes of the invention and should not be interpreted as limiting its scope. Examples Example 1: Ingredients and measurement methods Ingredients used

[0214] The following ingredients were used:

[0215] - MS POLYMER™ S303H marketed by KANEKA: poly(propylene oxide) with dimethoxysilane terminations of average number molar mass of 21 to 23 kg / mol, and a viscosity of 12.5 Pa.s;

[0216] - MS POLYMER™ SAX 725 marketed by KANEKA: poly(oxide of propylene) with dimethoxysilane terminations of mass average molar mass Mw of about 51 kg / mol and number average molar mass of about 41 kg / mol, and a viscosity of 87 Pa.s;

[0217] - DYNASYLAN® VTMO marketed by EVONIK: vinyltrimethoxysilane (No. CAS: 2768-02-7), moisture absorber;

[0218] - DYNASYLAN® AMMO marketed by EVONIK: (3-aminopropyl)trimethoxysilane (CAS No.: 13822-56-5), adhesion promoter;

[0219] - CALOFORT® SV14 marketed by Specialty Minerals: calcium carbonate fatty acid-coated precipitate, having an average particle size of 70 nm;

[0220] - OMYACARB 2T-AV marketed by OMYA: calcium carbonate (also designated GCC for "Ground Calcium carbonate") having a particle size d50 of 2.7 µm and a moisture content less than or equal to 0.2% by total weight of the OMYACARB 2T-AV;

[0221] - HAKUENKA® CCR-S10 marketed by OMYA: calcium carbonate fatty acid-coated precipitate, having an average particle size of 80 nm;

[0222] - RIASORB UV-123 marketed by RIANLON: bis(l-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate (CAS No.: 129757-67-1), hindered amine light stabilizer (HALS);

[0223] - 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);

[0224] - PRINTEX® 25 marketed by Orion: carbon black having an OAN of 45 mL / 100 g measured according to ASTM D-2414 method;

[0225] - ELFTEX® S5100 marketed by CABOT: carbon black having an OAN of 108 mL / 100 g measured according to ASTM D-2414 method;

[0226] - ELFTEX® S7100 marketed by CABOT: carbon black having an OAN of 117 + 6 mL / 100 g measured according to ASTM D-2414 method;

[0227] - SILQUEST A-LINK 600 marketed by MOMENTIVE: 4-amino-3,3-dimethylbutyltrimethoxysilane (CAS No.: 157923-74-5), non-yellowing adhesion promoter;

[0228] - NEOSTANN Sl marketed by KANEKA: silicic acid (H4SiO4), ester of tetraethyl, reaction products with bis(acetyloxy)dibutylstannane (CAS No.: 93925-43-0), crosslinking catalyst;

[0229] - TIB KAT 425 marketed by TIB CHEMICALS: mixture TIB KAT 232 (dioctyltin oxide) / silane, crosslinking catalyst;

[0230] - THIXATROL® AS 8053 marketed by ELEMENTIS: rheology agent micronized amide wax having an average diameter of less than 5 pm;

[0231] - CRAYVALLAC® SLX marketed by ARKEMA: wax rheology agent micronized amides (particle size less than 5 pm);

[0232] - Hexamoll® DINCH marketed by BASF: diisononyl ester of acid 1,2-cyclohexanedicarboxylic acid, plasticizer. Measurement methods

[0233] Tensile strength, elongation at break, modulus of elasticity and modulus at 100% were measured in accordance with ISO 37 (December 2005), at a constant speed of 500 mm / min.

[0234] In particular, the following conditions were applied:

[0235] A standard dumbbell-shaped test specimen, 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.

[0236] To prepare the dumbbell, the composition to be tested is applied in a Teflon mold, and the composition is left to crosslink for 14 days under standard conditions (23°C and 50% relative humidity).

[0237] The principle of the measurement consists of stretching a standard test specimen in a tensile testing machine, the movable jaw of which moves at a constant speed of 500 mm / minute, and recording:

[0238] - the elongation at break (expressed in %) is the elongation of the specimen cor responding to the stretching observed at the time of rupture,

[0239] - the modulus at 100% (in MPa) is the tensile stress corresponding to an al 100% length of the test tube,

[0240] - the modulus of elasticity (expressed in MPa) is the slope of the tangent at the origin of the curve showing tensile stress as a function of specimen elongation, and

[0241] - the tensile strength (in MPa) is the tensile stress at which occurs the rupture of the test tube.

[0242] The measurement is repeated for 5 test tubes, and the corresponding average of the results obtained is calculated.

[0243] Shear strength was measured according to the following method:

[0244] Two rectangular aluminum plates with dimensions: 100 mm x 25 mm x 2 mm are used. After cleaning both 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.

[0245] On the bonding area of ​​a first substrate plate thus materialized, the silylated polymer composition is applied, in an amount corresponding to a thickness of 2 mm. Then the bonding area of ​​the 2nd substrate plate is superimposed on the area thus coated, 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 sealant.

[0246] The resulting assembly specimen 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.

[0247] The two free ends of the specimen are pulled by means of a tensile machine at a constant speed of 50 mm / minute, until the assembly breaks, for which the applied stress is recorded.

[0248] The measurement is repeated for 3 assembly specimens, and the average of the shear stresses at failure (called shear strength) obtained is calculated.

[0249] It is also noted whether the break is of the cohesive type (break within the composition) or adhesive type (break at the composition / plate interface).

[0250] Example 2: effect of carbon black incorporation as a function of its OAN

[0251] In a reactor maintained under stirring, the comparative composition is prepared by mixing the ingredients in the proportions indicated in Table 1 below, in several steps according to the process described below.

[0252] The ingredients of step 1 are mixed at room temperature (approximately 23°C), at atmospheric pressure and at low stirring speed (sufficient to homogenize).

[0253] Next, 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 the mixing is carried out for 10 to 30 min.

[0254] Finally, the ingredients from step 3 are added under vacuum and the mixing is carried out at low stirring speed (sufficient to homogenize).

[0255] [Tables 1] Step Ingredient % by weight of total composition weight 1 MS POLYMER S303H 37 DYNASYLAN® VTMO 2.7 RIASORB123 0.4 2 TINUVIN 770 DF 0.2 CRAYVALLAC® SLX 3.5 CALOFORT SV14 45.5 OMYACARB 2T-AV 9.4 3 DYNASYLAN® AMMO 1 NEOSTANN Sl 0.3

[0256] Compositions 1b to le are prepared according to the same process as the comparative composition la and have the same composition, except that:

[0257] - 2% by weight of CALOFORT SV 14 are replaced by 2% by weight of PRINTEX 25, relative to the total weight of the composition, for the comparative composition 1b; - 5% by weight of CALOFORT SV 14 are replaced by 5% by weight of PRINTEX 25, in relation to the total weight of the composition, for the comparative composition; - 2% by weight of CALOFORT SV 14 are replaced by 2% by weight of ELFTEX S5100, relative to the total weight of the composition, for the com position Id according to the invention; - 5% by weight of CALOFORT SV 14 are replaced by 5% by weight of ELFTEX S5100, in relation to the total weight of the composition, for the composition according to the invention.

[0258] For example, comparative composition 1b has the same composition as the, except that it comprises 43.5% by weight of CALOFORT SV14 and 2% by weight of PRINTEX 25.

[0259] Carbon black (PRINTEX 25 or ELFTEX S5100) is also added during step 2 of the process.

[0260] The mechanical properties of compositions No. 1 to 4 (measured in accordance with Example 1) are summarized in Table 2 below.

[0261] [Tables2] Composition Comparative 1b Comparative Comparative Id Invention Invention Modulus at 100% (MPa) 2.3 2.5 2.6 2.9 3.2 Tensile Strength (MPa) 2.9 3 3.1 3.5 4 Elongation at Break (%) 180 200 200 230 220

[0262] Comparison of the results obtained for compositions 1a and 1b leads to the conclusion that the incorporation of PRINTEX 25 does not significantly increase the tensile strength of the composition, and allows a slight improvement in elongation at break (increase of 11%).

[0263] Furthermore, when a larger quantity of PRINTEX 25 is incorporated, this does not significantly increase the tensile strength of the composition, and does not influence its elongation at break (comparison of the results obtained for compositions 1b and le).

[0264] On the other hand, the tensile strength of composition Id (2% ELFTEX S5100) is 21% higher than that of composition la and its elongation at break has been improved by 28%, while the tensile strength of composition le (5% ELFTEX S5100) is 38% higher than that of composition la and its elongation at break has been improved by 22%.

[0265] 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 position, this effect not being obtained with the incorporation of PRINTEX 25 (carbon black having an OAN of 45 mL / 100 g).

[0266] Example 3: Comparative composition 2a not comprising a rheology agent

[0267] In a reactor maintained under stirring, the different ingredients of the comparative composition 2a are mixed in the proportions indicated in Table 3 below, in several steps according to the process below.

[0268] The ingredients of step 1 are mixed at room temperature (approximately 23°C), at atmospheric pressure and at low stirring speed (sufficient to homogenize).

[0269] Next, 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 the mixing is carried out for 10 to 30 min.

[0270] Finally, the ingredients from step 3 are added under vacuum and the mixing is carried out at low stirring speed (sufficient to homogenize)

[0271] [Tables3] Step Ingredient % by weight of total composition weight 1 MS POLYMER™ SAX 725 43.53 DYNASYLAN® VTMO 3.00 RIASORB UV-123 0.40 2 HAKUENKA® CCR-S10 45.32 TINUVIN 770 DF 0.20 ELFTEX® S7100 6.00 3 DYNASYLAN® AMMO 0.70 SILQUEST A-LINK 600 0.70 TIB KAT 425 0.15

[0272] Example 4: Comparative composition 2b not comprising a rheology agent

[0273] Comparative composition 2b is similar to comparative composition 2a, except that a plasticizer has been added (Hexamoll® DINCH).

[0274] In a reactor maintained under stirring, the different ingredients of the comparative composition 2b are mixed in the proportions indicated in Table 4 below. below, in several steps, according to the procedure described in Example 3.

[0275] [Tables4] Step Ingredient % by weight of total composition weight 1 MS POLYMER™ SAX 725 40.43 DYNASYLAN® VTMO 3.00 RIASORB UV-123 0.40 Hexamoll® DINCH 10.00 2 HAKUENKA® CCR-S10 38.32 TINUVIN 770 DF 0.20 ELFTEX® S7100 6.00 3 DYNASYLAN® AMMO 0.70 SILQUEST A-LINK 600 0.70 TIB KAT 425 0.25 Example 5: Composition 2c according to the invention

[0276] Composition 2c according to the invention is similar to the comparative composition 2b, except that a rheology agent has been added (THIXATROL® AS 8053).

[0277] 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 up to 50-55°C (corresponding to the activation temperature of THIXATROL® AS 8053) instead of 75-80°C.

[0278] [Tables5] Step 1 Ingredient % by weight of the total weight of the composition MS POLYMER™ SAX 725 38.43 DYNASYLAN® VTMO 3.00 RIASORB UV-123 0.40 Hexamoll® DINCH 10.00 2 HAKUENKA® CCR-S10 38.32 TINUVIN 770 DF 0.20 THIXATROL® AS 8053 2.00 ELFTEX® S7100 6.00 3 DYNASYLAN® AMMO 0.70 SILQUEST A-LINK 600 0.70 TIB KAT 425 0.25 Example 6: 2D composition according to the invention

[0279] Composition 2d is similar to composition 2c, except that a different rheology agent has been used (CRAYVALLAC® SLX).

[0280] In a reactor maintained under stirring, 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.

[0281] [Tableauxô] Step 1 Ingredient % by weight of total composition weight MS POLYMER™ SAX 725 38.43 DYNASYLAN® VTMO 3.00 RIASORB UV-123 0.40 Hexamoll® DINCH 10.00 HAKUENKA® CCR-S10 38.32 TINUVIN 770 DF 0.20 CRAYVALLAC® SLX 2.00 ELFTEX® S7100 6.00 DYNASYLAN® AMMO 0.70 SILQUEST A-LINK 600 0.70 TIB KAT 425 0.25

[0282] Example 7: Mechanical properties of compositions 2a to 2d

[0283] The mechanical properties of compositions 2a to 2d (measured in accordance with Example 1) are summarized in Table 7 below.

[0284] [Tables?] Composition 2a comparative 2b comparative 2c invention 2d invention Modulus of elasticity (MPa) 4.79 2.86 3.06 4.3 Modulus at 100% (MPa) 2.70 1.55 1.61 1.83 Elongation at break (%) 447 555 680 691 Tensile strength (MPa) 5.53 4.56 4.93 5.04 Shear strength (MPa) 2.1 3.81 3.6 3.32 Fracture face 90% adhesive 10% cohesive 100% cohesive 100% cohesive 100% cohesive

[0285] 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.

[0286] Indeed, compared with the comparative composition 2b which does not include 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%.

[0287] Compositions 2c and 2d according to the invention also have the advantage of exhibiting a 100% cohesive fracture face.

Claims

1.

2. Demands Composition includes: - a silylated polymer, - carbon black having an oil absorption rate (OAN) of at least 80 mL / 100 g, and - a rheology agent. Composition according to claim 1, wherein the silylated polymer comprises at least one, preferably at least two, al-koxysilane groups of formula (I): -If(R <MOR5)^ (!) in which: - R4 represents a linear or branched alkyl radical comprising 1 to 4 carbon atoms, and when p equals 2, the R4 radicals are either identical or different. - R5 represents a linear or branched alkyl radical comprising 1 to 4 carbon atoms, and when p is equal to 0 or 1, the R5 radicals are identical or different, two OR5 groups being able to be involved in the same ring, 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): Po in which: (n) P - O-—- R -- S il R (OR û A (neither) R4, R5 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, R1 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-, -NR7- or -S-, R7 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 (II'), (II”), (III') or (IV'): ¢8¾)¾ JR*juSÏ- R—«H-C—O — RXo— C—KH-R—NH-C—O — R 4-0 — G — NH-R—SKRXfOFA, „ p il T il il X h -p' O O O O (il’) i R; - NH - C— O- R24o- R^O-C- NH- R?™ Si(R4WOR*h.< O O (II”) (R^pCR4)^- R5- 0- Ra-[o- R^O- R’^ SKR4)p(OR5)^p (HD -^0^^^-8^-8^-0-8878^8.-0^0-840^0--^-8^-0170-70-840^-0-01-8-8870^--8-8^81(08^ H u l h H. X 4 (i “ (IV’) in which: - R1, R3, R4, R5, X, R7 and p have the same meaning as in formulas (II), (III) and (IV), - R2 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: - R2 represents an isopropylene radical, - R4 and R5 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 an amide wax and / or a castor oil derivative, preferably an amide wax.

8. Composition according to any one of claims 1 to 7, further comprising at least one adhesion promoter selected from amino-, mercapto- and epoxy-alkoxysilanes, preferably selected from aminoalkoxysilanes, more preferably from aminotrial-koxysilanes, and even more preferably from aminotrimethoxysilanes.

9. Composition according to claim 8, wherein the at least one adhesion promoter is a mixture of at least two promoters membership, preferably from two membership promoters.

10. Use of the composition according to any one of claims 1 to 9, 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.