Compositions comprising silylated polymers

Abstract

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

Description

Technical Field

[0001] The present invention relates to compositions comprising silyl-modified polymers and also to the use thereof, in particular for adhesive bonding and sealing. Background Art

[0002] There are various polymer-based compositions on the market that can be used in many fields, in particular as sealants. Sealants make it possible to assemble (or join or attach) two substrates that can be chosen from the most diverse materials and can also serve as sealed joints. Sealants provide the assembly thus obtained with advantageous mechanical properties of robustness, elasticity and / or flexibility and fluid tightness.

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

[0004] Some applications, in particular the attachment of glass sheets (such as windshields or windows) to the body of a vehicle, require polymer-based compositions to have specific mechanical properties, in particular high tensile strength and high elongation at break. In particular, it is important that the composition does not break during the impact to which it is subjected.

[0005] The compositions used on the market for replacement windshields are generally compositions based on isocyanate-terminated polyurethanes, which generally have high tensile strength and high elongation at break. When using said compositions to make components, the reaction of the isocyanate-reactive groups with water originating from the moisture in the air or from the substrates to be assembled is called a crosslinking reaction. The completion of this reaction, after a period of time known as the crosslinking time, enables the creation of a solid three-dimensional network that contributes to imparting the desired mechanical properties to the adhesive joint thus formed.

[0006] Compositions based on alkoxysilane-terminated polymers (also referred to as silyl-modified polymers) have the advantage of being isocyanate-free. These compositions therefore constitute an alternative to compositions based on isocyanate-terminated polyurethanes, which are preferred from a toxicological point of view.

[0007] The crosslinking reaction of these compositions based on silyl-modified polymers occurs in the presence of moisture by hydrolysis of the alkoxysilane groups carried by the polymer, followed by their condensation to form siloxane bonds (—Si—O—Si—) linking the polymer chains into a solid three-dimensional network.

[0008] However, it is difficult to obtain compositions based on silyl-modified polymers, especially sealants, having both high tensile strength and high elongation at break. In particular, compositions based on silyl-modified polymers generally have lower tensile strength and elongation at break than compositions based on isocyanate-terminated polyurethanes.

[0009] Therefore, there is a need to find compositions comprising silyl-modified polymers having improved tensile strength and elongation at break properties, in particular tensile strength and elongation at break properties similar to those of compositions based on isocyanate-terminated polyurethanes. Summary of the invention

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

[0011] - Silyl-modified polymers,

[0012] - carbon black having an oil absorption number (OAN) of at least 80 ml / 100 g, and

[0013] - Rheological agents.

[0014] Another subject of the invention is a method for assembling two substrates by adhesive bonding, comprising:

[0015] - applying the composition according to the invention as defined previously to at least one of the two substrates to be assembled; then

[0016] - physically bringing the two substrates into contact.

[0017] The invention also relates to an article, preferably a vehicle, obtainable according to the assembly method as defined above.

[0018] The invention also relates to a vehicle comprising a composition as defined in this description, said composition being in contact simultaneously with a first substrate and a second substrate of said vehicle.

[0019] The invention furthermore relates to the use of the composition according to the invention as a sealant, in particular as a sealing joint.

[0020] Finally, the invention relates to the use of the composition according to the invention for adhesive bonding and sealing.

[0021] Surprisingly, it has been found that the addition of a combination of a rheological agent and a carbon black having a high OAN to a silyl-modified polymer composition makes it possible to significantly improve the tensile strength and elongation at break properties of said composition.

[0022] The composition according to the invention is therefore particularly advantageous for attaching glass panes, such as windscreens or windows, to the body of a vehicle, in particular for replacing the windscreen of a vehicle. DETAILED DESCRIPTION

[0023] Therefore, the present invention relates to a composition comprising:

[0024] - Silyl-modified polymers,

[0025] - carbon black having an oil absorption number (OAN) of at least 80 ml / 100 g, and

[0026] - Rheological agents.

[0027] Silyl-modified polymers

[0028] "Silyl-modified polymer" is understood to mean a polymer comprising at least one alkoxysilane group. Preferably, the silyl-modified polymer comprises at least one alkoxysilane group located at the terminal end of the polymer.

[0029] The silyl-modified polymer is generally in the form of a more or less viscous liquid. Advantageously, the silyl-modified 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.

[0030] The viscosity of the silyl-modified polymer can be measured, for example, according to the Brookfield method at 23° C. and 50% relative humidity (spindle S28).

[0031] In the context of the present invention, ranges of values ​​are to be understood as meaning inclusive limit values. For example, the range "between 0% and 25%" specifically includes the values ​​0% and 25%.

[0032] Advantageously, the silyl-modified polymer comprises at least one, preferably at least two, alkoxysilane groups of formula (I):

[0033]

[0034] in:

[0035] -R 4 represents a linear or branched alkyl group comprising 1 to 4 carbon atoms, and when p is equal to 2, R 4 The groups are the same or different,

[0036] -R 5 represents a linear or branched alkyl group comprising 1 to 4 carbon atoms, and when p is equal to 0 or 1, R 5 The groups are the same or different, two OR 5The groups may be inserted into the same ring, and

[0037] - p is an integer equal to 0, 1 or 2, preferably equal to 0 or 1.

[0038] Preferably, the alkoxysilane group of the silyl-modified polymer has the formula (I), wherein:

[0039] -R 4 and R 5 each represents a methyl group, and

[0040] - p is equal to 0 or 1.

[0041] Advantageously, the silyl-modified polymer has a number average molar mass of 500 g / mol to 70,000 g / mol, preferably 4,000 g / mol to 60,000 g / mol, more preferably 10,000 g / mol to 50,000 g / mol.

[0042] The molar mass of a polymer can be measured by methods well known to those skilled in the art, for example by NMR or by size exclusion chromatography using polystyrene standards.

[0043] Advantageously, the silyl-modified polymer has formula (II), (III) or (IV):

[0044]

[0045] in:

[0046] -R 4 , R 5 and p have the same meanings as in the above formula (I),

[0047] - P represents a saturated or unsaturated polymeric radical having a linear or branched open chain or comprising one or more optional aromatic rings, 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,

[0048] -R 1 represents a saturated or unsaturated divalent hydrocarbon radical comprising 5 to 15 carbon atoms, having a linear or branched open chain, or comprising one or more optional aromatic rings,

[0049] -R 3 represents a linear or branched divalent alkylene group comprising 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms,

[0050] - X represents a member selected from –NH–, –NR 7 – or –S–,

[0051] -R 7 represents a linear or branched alkyl group comprising 1 to 20 carbon atoms and which may also comprise one or more heteroatoms,

[0052] - 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.

[0053] Advantageously, the silyl-modified polymer has formula (II), (III) or (IV), wherein P represents a polymer group selected from the group consisting of polyethers, polycarbonates, polyesters, polyolefins, polyacrylates, polyether polyurethanes, polyester polyurethanes, polyolefin polyurethanes, polyacrylate polyurethanes, polycarbonate polyurethanes, segmented polyether / polyester polyurethanes and polysiloxanes, preferably selected from polyethers, polyurethanes and mixtures thereof, more preferably selected from polyethers.

[0054] Preferably, the silyl-modified polymer has formula (II'), (II''), (III') or (IV'):

[0055]

[0056] in:

[0057] -R 1 , R 3 , R 4 , R 5 ,X,R 7 and p have the same meanings as in formulae (II), (III) and (IV),

[0058] -R 2 represents a linear or branched, saturated or unsaturated divalent hydrocarbon radical, which optionally comprises one or more heteroatoms such as oxygen, nitrogen, sulfur, silicon, and optionally comprises one or more ionic groups,

[0059] - n is an integer, preferably n is such that the number average molar mass of the silyl-modified polymer is 500 g / mol to 70,000 g / mol, more preferably 4,000 g / mol to 60,000 g / mol, even more preferably 10,000 g / mol to 50,000 g / mol.

[0060] In the silyl-modified polymers of formula (II'), (II''), (III') and (IV') defined above, when R 2 When the group includes one or more heteroatoms, the heteroatoms are not present at the chain ends. In other words, the divalent R bonded to the adjacent oxygen atom of the silyl-modified polymer 2The free valences of the radicals are each derived from a carbon atom. 2 The main chain of the radical is terminated at each of the two ends by a carbon atom which then has a free valence.

[0061] According to one embodiment, the silyl-modified polymer is obtained from a polyol selected from the group consisting of polyether polyols, polyester polyols, polycarbonate polyols, polyacrylate polyols, polysiloxane polyols, polyolefin polyols and mixtures thereof; preferably from a diol selected from the group consisting of polyether diols, polyester diols, polycarbonate diols, polyacrylate diols, polysiloxane diols, polyolefin diols and mixtures thereof; more preferably from a polyether diol. In the case of the polymers of formula (II'), (II''), (III') and (IV') above, such a diol may be selected from the group consisting of formula HO-R 2 -OH or H-[OR 2 ] n -OH means, where R 2 has the same meaning as in formulae (II'), (II''), (III') and (IV').

[0062] In particular, in the silyl-modified polymer of formula (IV') defined above, R 2 The groups may be the same or different, that is, the silyl-modified polymer of formula (IV') may be composed of the same or different HO-R 2 Silyl-modified copolyurethanes obtained from -OH diols.

[0063] According to one embodiment, when the silyl-modified polymer has formula (II') or (IV'), R 2 The radical may be selected from the following divalent radicals, the following formula of which shows two free valencies:

[0064] - Polypropylene glycol derivatives:

[0065] - Polyester diol derivatives:

[0066] - Derivatives of polybutadiene glycol:

[0067] - Polyacrylate diol derivatives:

[0068] - Polysiloxanediol derivatives:

[0069] in:

[0070] - q represents an integer such that R 2The number average molar mass of the radical is in the range of 100 g / mol to 48600 g / mol, preferably 300 g / mol to 18600 g / mol, more preferably 500 g / mol to 12600 g / mol,

[0071] - r and s represent zero or non-zero integers such that R 2 The number average molar mass of the group 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 of r + s is not zero,

[0072] -Q 1 represents a saturated or unsaturated, linear or branched, aliphatic or aromatic divalent alkylene radical preferably having 1 to 18 carbon atoms, more preferably 1 to 8 carbon atoms,

[0073] -Q 2 represents a linear or branched divalent alkylene group preferably having 2 to 36 carbon atoms, more preferably 1 to 8 carbon atoms,

[0074] -Q 3 , Q 4 , Q 5 , Q 6 , Q 7 and Q 8 Independently of one another represent a hydrogen atom or an alkyl, alkenyl or aromatic group preferably containing 1 to 12 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms.

[0075] According to a specific embodiment, when the silyl-modified polymer has the formula (IV'), the silyl-modified polymer may be composed of different HO-R 2 -OH diols are obtained, where one R 2 The group can be selected from the above divalent groups (derivatives of polypropylene glycol, polyester glycol, polybutadiene glycol, polyacrylate glycol, polysiloxane glycol), and one of the R 2 The group is an ionic divalent group of the formula:

[0076]

[0077] in:

[0078] - x and y, which may be the same or different, are integers ranging from 1 to 8,

[0079] - z is an integer ranging from 0 to 8,

[0080] -R 0represents a hydrogen atom or an alkyl group containing 1 to 18 carbon atoms, and

[0081] - R, R' and R'' may be identical or different and each represent a saturated, unsaturated or aromatic hydrocarbon radical, optionally including heteroatoms selected from N, O and S; R, R' and R'' are also such that the tertiary amine of formula N(R)(R')(R") is a linear, branched or cyclic amine or polyamine having a number average molar mass in the range of 59 to 6000 g / mol and having a pKa greater than 8.

[0082] According to one embodiment, R 1 is selected from the following divalent groups, the following formula of which shows two free valencies:

[0083] a) Divalent groups derived from isophorone diisocyanate (IPDI):

[0084]

[0085] b) Divalent radicals derived from dicyclohexylmethane diisocyanate (H12MDI):

[0086]

[0087] c) Divalent radicals from the 2,4- and 2,6-isomers of toluene diisocyanate (TDI):

[0088]

[0089] d) Divalent radicals derived from the 4,4'- and 2,4'-isomers of diphenylmethane diisocyanate (MDI):

[0090]

[0091] e) Divalent group derived from hexamethylene diisocyanate (HDI): -(CH2)6-

[0092] f) Divalent groups derived from meta-xylylene diisocyanate (m-XDI):

[0093] .

[0094] According to a preferred embodiment, the silyl-modified polymer has the formula (II'') or (III'), preferably (III'), and R 2 The radical preferably represents a linear or branched divalent alkylene radical comprising 2 to 4 carbon atoms, more preferably a linear or branched divalent alkylene radical comprising 3 carbon atoms, even more preferably an isopropylidene radical (formula -CH2-CH(CH3)-).

[0095] According to a particularly preferred embodiment, the silyl-modified polymer is a polymer of formula (III'), wherein:

[0096] -R 2 represents an isopropylidene group,

[0097] -R 4 and R 5 each represents a methyl group, and

[0098] - p is equal to 1.

[0099] The polymers of formula (II), (II') and (II") can be obtained, for example, according to the methods described in documents EP 2 336 208 and WO 2009 / 106699. Among the polymers corresponding to formula (II), mention may be made of:

[0100] - Geniosil STP-E10 (available from Wacker Chemie): a polyether of formula (II'') comprising two groups of formula (I) of the dimethoxy type (p is equal to 1, and R 4 and R 5 represents a methyl group), having a number average molar mass of 8889 g / mol, wherein R 3 represents a methyl group;

[0101] - Geniosil STP-E30 (available from Wacker Chemie): a polyether of formula (II'') comprising two groups of formula (I) of the dimethoxy type (p is equal to 1, and R 4 and R 5 represents a methyl group), having a number average molar mass of 14493 g / mol, wherein R 3 represents a methyl group;

[0102] -Desmoseal S XP 2636 (available from Bayer): a radical of formula (I) comprising two trimethoxy groups (p equal to 0 and R 5 represents a methyl group), having a number average molar mass of 15038 g / mol, wherein R 3 It represents n-propylene.

[0103] The polymers of formula (III) or (III') can be obtained by hydrosilylation of polyether diallyl ethers according to the method described, for example, in document EP 1 829 928. Among the polymers corresponding to formula (III), mention may be made of:

[0104] - Polymer MS SAX 350 (available from Kaneka), which corresponds to a group of formula (I) comprising two dimethoxy groups (p is equal to 1, and R 4 and R 5 denotes a methyl group), having a number average molar mass in the range of 14000 to 16000 g / mol;

[0105] - Polymer MS SAX 260 (available from Kaneka), which corresponds to a group of formula (I) comprising two dimethoxy groups (p is equal to 1, and R 4 and R 5 represents a methyl group), having a number average molar mass of 16000 to 18000 g / mol, wherein R 3 represents an ethyl group;

[0106] - polymer MS S303H (available from Kaneka) corresponding to a group of formula (I) comprising two dimethoxy types (p equal to 1 and R 4 represents a methyl group) having a number average molecular weight of 21000 to 23000 g / mol;

[0107] - Polymer MS SAX 725 (available from Kaneka), which corresponds to a group of formula (I) comprising two dimethoxy groups (p equals 1 and R 4 and R 5 represents a methyl group) 2 represents an isopropylidene group), having a number average molar mass of about 41 kg / mol.

[0108] The polymers of formula (IV) or (IV') can be obtained, for example, by reacting a polyol with one or more diisocyanates and subsequently with an aminosilane or mercaptosilane. The method for preparing polymers of formula (IV) or (IV') is described, for example, in document EP 2 583 988. A person skilled in the art will know how to adapt the production method described in this document when using different types of polyols. Among the polymers corresponding to formula (IV), mention may be made of:

[0109] - SPUR+ 1050MM (available from Momentive): includes two groups of formula (I) of the trimethoxy type (p is equal to 0 and R 5 represents a methyl group), having a number average molar mass of 16393 g / mol, wherein R 3 represents an n-propyl group;

[0110] - SPUR+ Y-19116 (available from Momentive): a group of formula (I) comprising two trimethoxy groups (p equal to 0 and R 5 represents a methyl group) having a number average molar mass in the range of 15000 to 17000 g / mol, wherein R 3 represents an n-propyl group.

[0111] In the composition according to the invention, the content of silyl-modified polymer may range from 5% to 60% by weight, 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, relative to the total weight of the composition.

[0112] Carbon Black

[0113] The carbon black in the composition of the present invention has an oil absorption number (OAN) of at least 80 ml / 100 g.

[0114] The OAN of carbon black corresponds to the volume (in ml) of dibutyl phthalate (DBP) oil absorbed by 100 g of carbon black.

[0115] OAN can be measured, for example, according to ASTM D-2414 method and using DBP oil.

[0116] Unless otherwise stated, the standards referred to throughout this application are those in effect on the filing date of this application.

[0117] The carbon black used in the present invention is generally referred to as "structural" carbon black, and is different from the carbon black generally used as a pigment, particularly due to its high OAN.

[0118] Specifically, the carbon black used as a pigment is of lower quality and has a lower OAN than the carbon black used in the present invention.

[0119] Examples of carbon black used as a pigment are PRINTEX 25 (sold by Orion), which has 45 ml / 100 g of OAN.

[0120] Examples of carbon black that can be used in the present invention are ELFTEX S7100 and ELFTEX S5100 (sold by CABOT), which have OAN of about 117 and 108 ml / 100 g, respectively.

[0121] The term "about X" is intended to mean plus or minus 10% of the value of X.

[0122] Preferably, the carbon black has an OAN of at least 90 ml / 100 g, more preferably at least 100 ml / 100 g, even more preferably at least 110 ml / 100 g.

[0123] Advantageously, in the composition according to the invention, the content of carbon black is at least 2% by weight, 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% relative to the total weight of the composition.

[0124] Rheological agent

[0125] Rheological agents make it possible to adjust the rheological properties of the compositions according to the invention.

[0126] By way of example, mention may be made of any rheological agent customarily used in the field of sealant compositions.

[0127] Advantageously, the rheological agent is one or more thixotropic agents, for example solid at 23° C. and / or having a viscosity greater than 200 mPa.s at 23° C. according to standard ISO 12058-1, preferably solid at 23° C. Thixotropic agents generally influence the thixotropy of the composition. Thixotropy is the property that some compositions become less viscous when a constant force is applied (e.g. shear under constant stress), and after the stress ceases, the viscosity returns to its initial state after a suitable period of time. The greater the force, the lower the viscosity.

[0128] In particular, one or more rheological agents selected from the group consisting of:

[0129] - PVC plastisols, corresponding to suspensions of PVC in plasticizers 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 publication Polyurethane Sealants, Robert M. Evans, ISBN 087762-998-6;

[0130] - fumed silica, such as HDK sold by Wacker N20;

[0131] - urea derivatives obtained by the reaction of aromatic diisocyanate monomers, such as 4,4'-MDI, with aliphatic amines, such as butylamine. The preparation of such urea derivatives is described in particular in patent application FR 1 591 172;

[0132] - waxes derived from castor oil, such as THIXCIN available from Elementis R,

[0133] - Amide waxes, preferably micronized amide waxes, such as CRAYVALLAC sold by Arkema SLX、CRAYVALLAC SLW or CRAYVALLAC SUPER, or THIXATROL available from Elementis AS8053 or THIXATROL MAX (EC No.: 432-430-3), or RHEOBYK 7503 sold by BYK.

[0134] These rheological agents are thixotropic agents.

[0135] The term "wax derived from castor oil" is understood to mean wax obtained from castor oil, in particular hydrogenated castor oil. The wax derived from castor oil is solid at 23°C.

[0136] The term "amide wax" is understood to mean a wax comprising one or more compounds having at least one amide group. In particular, amide waxes are obtainable from fatty acids (eg ricinoleic acid) and (di)amines. Amide waxes are solid at 23°C.

[0137] Preferably, the rheological agent is an amide wax and / or a wax derived from castor oil, more preferably an amide wax.

[0138] 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 μm, preferably less than 100 μm, more preferably less than 10 μm.

[0139] The average particle size advantageously corresponds to the d50 particle size, ie the maximum dimension of the 50% by volume smallest particles, and can be measured with a laser particle size analyzer, in particular by laser diffraction on a MALVERN apparatus (for example according to the NF ISO 13320 standard).

[0140] The rheological agent of amide wax type may be heat-activatable, that is to say may require a temperature above ambient temperature (23° C.) to activate it (in particular to activate its rheological properties, in particular its thixotropic properties) during the preparation of the composition according to the invention.

[0141] The activation temperature depends on the rheological agent.

[0142] For example, THIXATROL AS8053 is generally activated at 50°C to 55°C, and CRAYVALLAC SLX is generally activated at a temperature of 75°C to 80°C.

[0143] Advantageously, in the composition according to the invention, the content of the rheological agent ranges from 0.2% to 20% by weight, preferably from 1% to 10% by weight, more preferably from 1% to 5% by weight relative to the total weight of the composition.

[0144] Adhesion Promoters

[0145] The composition according to the invention may also comprise at least one adhesion promoter.

[0146] Advantageously, the adhesion promoter is selected from amino-, mercapto- and epoxy-alkoxysilanes, preferably from aminoalkoxysilanes, more preferably from aminotrialkoxysilanes, even more preferably from aminotrimethoxysilanes.

[0147] As an example of epoxyalkoxysilane, mention may be made of (3-glycidyloxypropyl)trimethoxysilane (also known as GLYMO).

[0148] Advantageously, the aminotrimethoxysilane is selected from 4-amino-3,3-dimethylbutyltrimethoxysilane (for example Silquest A-Link 600 sold by Momentive), (3-aminopropyl)trimethoxysilane (for example Dynasylan AMMO) and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (e.g. Dynasylan Preferably, the aminotrimethoxysilane is formed from 4-amino-3,3-dimethylbutyltrimethoxysilane and (3-aminopropyl)trimethoxysilane.

[0149] Advantageously, the composition according to the invention comprises at least one adhesion promoter.

[0150] According to a preferred embodiment, the at least one adhesion promoter is a mixture of at least two adhesion promoters, preferably two adhesion promoters.

[0151] According to this preferred embodiment, the adhesion promoter is selected from aminoalkoxysilanes, preferably aminotrialkoxysilanes, more preferably aminotrimethoxysilane. Preferably, the adhesion promoter is a mixture of two adhesion promoters selected from the following: 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.

[0152] According to a preferred embodiment in which the adhesion promoter is a mixture of two adhesion promoters, the (first adhesion promoter) / (second adhesion promoter) weight ratio is advantageously from 0.25 to 4, preferably from 0.5 to 2, more preferably from 0.7 to 1.5, for example equal to 1.

[0153] In the composition according to the invention, the content of the adhesion promoter may range from 0.2 to 5 wt %, preferably from 0.5 to 3 wt %, more preferably from 1.0 to 2.0 wt %, relative to the total weight of the composition.

[0154] filler

[0155] Advantageously, the composition according to the invention further comprises a filler.

[0156] Preferably, the filler is selected from the group consisting of mineral fillers, organic fillers and mixtures thereof, more preferably mineral fillers.

[0157] Advantageously, the mineral filler is formed of clay, quartz, hollow mineral microspheres and carbonate fillers.

[0158] Among the hollow mineral microspheres, mention may be made of hollow glass microspheres, and more particularly those made of soda-lime borosilicate or aluminosilicate.

[0159] Preferably, the mineral filler is formed by a carbonate filler.

[0160] According to a preferred embodiment, the composition according to the present invention further comprises a carbonate filler, advantageously the carbonate filler is selected from alkali metal or alkaline earth metal carbonates and mixtures thereof, preferably the carbonate filler comprises calcium carbonate, more preferably, the carbonate filler is chalk or calcium carbonate coated with a fatty acid, even more preferably precipitated calcium carbonate coated with a fatty acid.

[0161] When calcium carbonate is coated with fatty acids, this makes it possible to impart all or part of the hydrophobicity to the calcium carbonate particles. In addition, the coating of fatty acids acts as a hydrophobic coating that can prevent calcium carbonate from absorbing the components of the composition and render them ineffective. The hydrophobic coating of calcium carbonate can account for 0.1 wt % to 3.5 wt %, relative to the gross weight of calcium carbonate.

[0162] Preferably, the fatty acid coating the calcium carbonate comprises or consists of more than 50% by weight of stearic acid, relative to the total weight of said fatty acids.

[0163] Examples of non-precipitated calcium carbonates coated with fatty acids that may be mentioned include OMYACARB 2T-AV or OMYABLH (sold by OMYA) or CALATEM C16T (sold by Provençale).

[0164] Examples of precipitated calcium carbonate coated with fatty acids that may be mentioned include HAKUENKA CCR-S10 (sold by OMYA) or CALOFORT (Sold by Specialty Minerals).

[0165] Advantageously, the organic filler is formed of polyvinyl chloride (PVC), polyolefins, rubber, ethylene / vinyl acetate (EVA), expandable or non-expandable hollow thermoplastic polymer microspheres (e.g. hollow vinylidene chloride / acrylonitrile microspheres) and aramid fibers (e.g. Kevlar ), preferably PVC.

[0166] Advantageously, the average particle size of the filler is from 10 nm to 400 μm, preferably from 20 nm to 100 μm, more preferably from 30 nm to 1 μm, even more preferably from 40 nm to 300 nm.

[0167] The average particle size advantageously corresponds to the d50 particle size, ie the maximum dimension of the 50% by volume smallest particles, and can be measured with a laser particle size analyzer, in particular by laser diffraction on a MALVERN apparatus (for example according to the NF ISO 13320 standard).

[0168] Advantageously, the filler content ranges from 10% to 80% by weight, preferably from 20% to 60% by weight, more preferably from 30% to 50% by weight, even more preferably from 35% to 40% by weight, relative to the total weight of the composition.

[0169] Crosslinking catalyst

[0170] The composition according to the invention may also comprise a crosslinking catalyst.

[0171] The catalyst may be any catalyst known to the skilled person for silanol condensation. Examples of such catalysts that may be mentioned include:

[0172] - organic derivatives of titanium such as titanium acetylacetonate (e.g. TYZOR sold by Dorf Ketal AA75),

[0173] - Aluminum, for example aluminum chelates (e.g. K-KAT sold by King Industries 5218),

[0174] - amines, for example 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 2,2'-dimorpholinodiethyl ether (DMDEE) or 1,4-diazabicyclo[2.2.2]octane (DABCO),

[0175] - Catalysts based on zinc carboxylate and DBU (e.g. K-KAT sold by King Industries 670),

[0176] - tin-based catalysts, for example 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 oxide or dibutyltin oxide. Mention may be made, for example, of NEOSTANN S-1 (sold by KANEKA), or TIB KAT 425 or TIB KAT 423 (sold by TIB CHEMICALS),

[0177] - Guanidine derivatives such as 1-(o-tolyl)biguanide (CAS No.: 93-69-6), for example Rhenocure 1000 C (sold by RheinChemie Additives).

[0178] Preferably, the crosslinking catalyst is a tin-based catalyst, preferably selected from compounds derived from dioctyltin and dibutyltin, more preferably derived from dioctyltin oxide or dibutyltin oxide.

[0179] In the composition according to the invention, the content of crosslinking catalyst may range from 0.01% to 5% by weight, 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, relative to the total weight of the composition.

[0180] The composition according to the invention may 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 functional groups. Mention may be made, for example, of tetraethoxysilane (e.g. WACKER TES 28 or TES 40 WN) or 1,2-bis(triethoxysilyl)ethane (e.g. Dynasylan BTSE).

[0181] In the composition according to the invention, the content of the crosslinking cocatalyst may range from 0.01 to 5 wt %, preferably from 0.05 to 2 wt %, more preferably from 0.1 to 1 wt %, relative to the total weight of the composition.

[0182] Other additives

[0183] The composition according to the present invention may further comprise at least one additive selected from the group consisting of plasticizers, moisture absorbers, solvents, UV stabilizers and mixtures thereof.

[0184] Advantageously, the composition according to the invention comprises a mixture of additives chosen from plasticizers, hygroscopic agents, solvents and UV stabilizers (or antioxidants).

[0185] In the composition according to the invention, the total content of additives may range from 0.5 to 30% by weight, preferably from 5 to 25% by weight, more preferably from 10 to 20% by weight, relative to the total weight of the composition.

[0186] Advantageously, the composition according to the invention comprises a plasticizer. A plasticizer is different from a rheological agent in that the properties of a composition comprising a plasticizer will be the same when stress is applied (e.g. shear) or in the absence of stress. On the other hand, if stress is applied, the properties of a composition comprising a rheological agent will be different. A plasticizer can be used to adjust viscosity (like a solvent).

[0187] The plasticizer may be any plasticizer commonly used in the field of sealant compositions.

[0188] Preferably, the plasticizer is selected from:

[0189] - diisodecyl phthalate (e.g. PALATINOL DIDP),

[0190] - diisononyl phthalate (DINP) (e.g. PALATINOL N),

[0191] - Alkyl sulfonates of phenol (e.g. MESAMOLL sold by LANXESS ),

[0192] - diisononyl 1,2-cyclohexanedicarboxylate (e.g. HEXAMOLL DINCH ),and

[0193] - Pentaerythritol tetravalerate (e.g. PEVALEN® sold by PERSTORP TM ).

[0194] More preferably, the plasticizer is diisononyl-1,2-cyclohexanedicarboxylate.

[0195] Advantageously, the plasticizer content ranges from 2% to 25% by weight, preferably from 5% to 20% by weight, more preferably from 7% to 15% by weight, relative to the total weight of the composition.

[0196] The composition according to the invention may also 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 ambient temperature (a temperature of about 23° C.). The volatile solvent may, for example, be chosen from alcohols that are volatile at ambient temperature, such as ethanol or isopropanol. The volatile solvent makes it possible, for example, to reduce the viscosity of the composition and to make the composition easier to apply. The volatile nature of the solvent makes it possible for the joint obtained after the composition has cured to no longer contain the solvent. Thus, the solvent, for example, has no negative effect on the hardness of the joint.

[0197] Advantageously, the composition according to the invention comprises up to 3.5% by weight of a hygroscopic agent, relative to the total weight of the composition, which may be chosen from vinyltrimethoxysilanes (for example Dynasylan® sold by Evonik) and Silane®. VTMO), propyltrimethoxysilane (e.g., Dynasylan PTMO), vinyltriethoxysilane (VTEO), alkoxyarylsilanes (for example GENIOSIL XL 70), p-toluenesulfonyl isocyanate (PTSI) and calcium oxide.

[0198] Preferably, the moisture absorbent is selected from vinyltrimethoxysilane, vinyltriethoxysilane and alkoxyarylsilane, more preferably vinyltrimethoxysilane.

[0199] 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 due to reaction with oxygen that is easily formed by the action of heat or light. These compounds may include antioxidants that are able to capture free radicals.

[0200] Advantageously, the UV stabilizer (or antioxidant) is selected from hindered benzotriazoles, benzophenones, phenols and amines, such as bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate (CAS No. 41556-26-7), 1,2,2,6,6-pentamethyl-4-piperidinyl sebacate methyl ester (CAS No. 82919-37-7), octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 4,4'-bis( -dimethylbenzyl)diphenylamine and mixtures thereof. Mention may be made, for example, of the products IRGANOX 1076, TINUVIN 292. TINUVIN 765 or TINUVIN 770 DF, RIASORB UV-123 sold by RIANO, AddWorks sold by Clariant IBC 760, and OKABEST CLX 50 sold by OKA.

[0201] Preferably, the UV stabilizer (or antioxidant) is selected from hindered phenols and amines, such as bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 4,4'-bis( -dimethylbenzyl)diphenylamine, and mixtures thereof.

[0202] According to one embodiment, the UV stabilizer (or antioxidant) is bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate and 4,4′-bis( -dimethylbenzyl)diphenylamine mixture.

[0203] Other characteristics of the composition according to the invention

[0204] According to one embodiment, the composition according to the invention comprises:

[0205] - 5% to 60% by weight of a silyl-modified polymer, relative to the total weight of the composition,

[0206] - 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,

[0207] - 0.2% to 20% by weight of a rheological agent (advantageously a thixotropic agent), relative to the total weight of the composition,

[0208] - 0.2% to 5% by weight of an adhesion promoter, relative to the total weight of the composition,

[0209] - 10% to 80% by weight of fillers, relative to the total weight of the composition,

[0210] - 0.01% to 5% by weight of a crosslinking catalyst, relative to the total weight of the composition,

[0211] - optionally 0.01% to 5% by weight of a crosslinking co-catalyst, relative to the total weight of the composition, and

[0212] - 0.5% to 30% by weight, relative to the total weight of the composition, of one or more additives chosen from plasticizers, hygroscopic agents, solvents and UV stabilizers.

[0213] Preferably, the composition according to the invention consists essentially of the above-mentioned ingredients. The term "consisting essentially of" is understood to mean that the composition according to the invention comprises less than 5% by weight, preferably less than 2% by weight, even more preferably less than 1% by weight of ingredients other than the above-mentioned ingredients, relative to the total weight of the composition.

[0214] The components and specific contents of the present embodiment are as described above, including the embodiment.

[0215] According to a specific embodiment, the composition according to the present invention comprises:

[0216] - 35% to 40% by weight of a silyl-modified polymer, relative to the total weight of the composition, preferably a polymer of formula (III'),

[0217] - 6% to 15% by weight of carbon black having an OAN of at least 80 ml / 100 g, preferably at least 110 ml / 100 g, relative to the total weight of the composition,

[0218] - 1% to 5% by weight of a rheological agent, relative to the total weight of the composition, the rheological agent being an amide wax,

[0219] - 1.0% to 2.0% by weight of an adhesion promoter, relative to the total weight of the composition, chosen from aminotrimethoxysilane,

[0220] - 35% to 40% by weight of a filler, relative to the total weight of the composition, said filler being precipitated calcium carbonate coated with a fatty acid,

[0221] - 0.1% to 0.8% by weight of a crosslinking catalyst, relative to the total weight of the composition, said crosslinking catalyst being a tin-based catalyst,

[0222] - optionally 0.1% to 1% by weight of a crosslinking co-catalyst, relative to the total weight of the composition, said crosslinking co-catalyst being an organic polyester derived from silicic acid, and

[0223] - 10% to 20% by weight of one or more additives chosen from plasticizers, hygroscopic agents, solvents and UV stabilizers, relative to the total weight of the composition.

[0224] Preferably, the composition according to the invention consists essentially of the above ingredients.

[0225] The components and specific contents of the present embodiment are as described above, including the embodiment.

[0226] 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.

[0227] 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%.

[0228] According to a preferred embodiment, the composition according to the present 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%.

[0229] 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 according to standard ISO 37 (December 2005), preferably at a constant speed equal to 500 mm / minute.

[0230] In particular, tensile strength and elongation at break can be measured as described in Example 1 below.

[0231] Preparation of the composition according to the invention

[0232] The composition according to the invention can be prepared by simply mixing its ingredients.

[0233] According to a preferred embodiment, the composition according to the present invention is prepared according to the following method:

[0234] - 1) mixing the silyl-modified polymer with any liquid additives such as plasticizers, solvents, hygroscopic agents and UV stabilizers (or antioxidants) in a suitable container, preferably at a temperature of 18°C ​​to 28°C and atmospheric pressure, and then

[0235] - 2) dispersing carbon black having an OAN of at least 80 ml / 100 g and any other solid ingredients such as rheological agents, fillers and solid additives such as UV stabilizers (or antioxidants) in the aforementioned liquid mixture for a period of time required to obtain a homogeneous mixture, and then

[0236] - 3) Add any remaining liquid ingredients such as adhesion promoters and catalysts and homogenize the medium.

[0237] Preferably, step 2) is performed at a pressure below atmospheric pressure, more preferably at a pressure of less than 50 kPa, even more preferably at a pressure of less than 20 kPa.

[0238] 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 rheological agent, the mixing of the solid ingredients is advantageously carried out at a temperature at which the rheological agent is activated.

[0239] Preferably, step 3) is carried out at a pressure and temperature approximately equal to the pressure and temperature used in step 2).

[0240] An example of the preparation of a composition according to the invention is described in Example 2.

[0241] Other subjects of the present invention

[0242] Another subject of the invention is a method for assembling two substrates by adhesive bonding, comprising:

[0243] - applying the composition according to the invention as defined above to at least one of the two substrates to be assembled; then

[0244] - physically bringing the two substrates into contact.

[0245] The substrates involved are varied and are preferably selected from concrete, metals such as aluminium and / or steel, and glass.

[0246] According to a preferred embodiment, one of the substrates is steel (eg a part of the body of a vehicle) and the other substrate is glass (eg a glass pane, such as a windshield or a window).

[0247] The invention also relates to an article, preferably a vehicle, obtainable according to the assembly method as defined above.

[0248] The invention also relates to a vehicle comprising a composition as defined in this description, said composition being in contact simultaneously with a first substrate and a second substrate of said vehicle, preferably with a part of the bodywork and a glass pane, such as a windscreen, of the vehicle.

[0249] The invention furthermore relates to the use of the composition according to the invention as a sealant, in particular as a sealing joint.

[0250] Finally, the present invention relates to the use of a composition according to the invention for adhesive bonding and sealing, in particular in the field of building construction, transport, such as road, sea, rail or air transport, and shipbuilding, preferably in the field of road, sea, rail or air transport, in particular for attaching glass panes, such as windshields or windows, to the body of a vehicle, preferably for replacing the windshield of a vehicle.

[0251] All embodiments described above can be combined with one another. In particular, the various above-described components of the composition and in particular the preferred embodiments of the composition can be combined with one another.

[0252] The following examples are given purely for the purpose of illustrating the present invention and are not to be construed as limiting the scope thereof.

[0253] Example

[0254] Example 1 : Ingredients and Measurement Methods

[0255] Ingredients used

[0256] Use the following ingredients:

[0257] - MS POLYMER sold by KANEKA TM S303H: dimethoxysilane-terminated poly(propylene oxide) having a number average molar mass of 21 to 23 kg / mol and a viscosity of 12.5 Pa.s;

[0258] - MS POLYMER sold by KANEKA TM SAX 725: dimethoxysilane-terminated poly(propylene oxide) having a weight-average molar mass Mw of about 51 kg / mol and a number-average molar mass of about 41 kg / mol and a viscosity of 87 Pa.s;

[0259] - DYNASYLAN marketed by Evonik VTMO: Vinyltrimethoxysilane (CAS No.: 2768-02-7), desiccant;

[0260] - DYNASYLAN marketed by Evonik AMMO: (3-aminopropyl)trimethoxysilane (CAS No.: 13822-56-5), adhesion promoter;

[0261] - CALOFORT sold by Specialty Minerals SV14: precipitated calcium carbonate coated with fatty acids, with an average particle size of 70 nm;

[0262] - OMYACARB 2T-AV sold by OMYA: calcium carbonate (also called 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% relative to the total weight of OMYACARB 2T-AV;

[0263] - HAKUENKA sold by OMYA CCR-S10: precipitated calcium carbonate coated with fatty acids, with an average particle size of 80 nm;

[0264] - RIASORB UV-123 sold by RIANLON: bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate (CAS No. 129757-67-1), hindered amine light stabilizer (HALS);

[0265] - TINUVIN 770 DF sold by BASF: bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate (CAS No. 52829-07-9), hindered amine light stabilizer (HALS);

[0266] - PRINTEX sold by Orion 25: Carbon black having an OAN of 45 ml / 100 g measured according to ASTM D-2414 method;

[0267] - ELFTEX sold by CABOT S5100: a carbon black having an OAN of 108 ml / 100 g measured according to ASTM D-2414 method;

[0268] - ELFTEX sold by CABOT S7100: carbon black having an OAN of 117 ± 6 ml / 100 g measured according to ASTM D-2414 method;

[0269] - SILQUEST A-link 600 sold by MOMENTIVE: 4-amino-3,3-dimethylbutyltrimethoxysilane (CAS No. 157923-74-5), a non-yellowing adhesion promoter;

[0270] - NEOSTANN S-1 sold by KANEKA: silicic acid (H4SiO4), tetraethyl ester, reaction products with bis(acetoxy)dibutylstannane (CAS No. 93925-43-0), crosslinking catalyst;

[0271] - TIB KAT 425 sold by TIB CHEMICALS: TIB KAT 232 (dioctyltin oxide) / silane mixture, crosslinking catalyst;

[0272] - THIXATROL sold by Elementis AS 8053: Micronized amide wax rheological agent with an average diameter of less than 5 µm;

[0273] - CRAYVALLAC marketed by Arkema SLX: micronized amide wax rheological agent (particle size less than 5 μm);

[0274] - Hexamoll sold by BASF DINCH: diisononyl 1,2-cyclohexanedicarboxylate, plasticizer.

[0275] Measurement method

[0276] The tensile strength, elongation at break, modulus of elasticity and 100% modulus were measured according to standard ISO 37 (December 2005) at a constant speed equal to 500 mm / min.

[0277] In particular, the following conditions apply:

[0278] A standard test specimen of dumbbell shape type 1 was used as indicated in the international standard ISO 37 (December 2005). The narrow part of the dumbbell used had a length of 33 mm, a width of 6 mm and a thickness of 2 mm.

[0279] To prepare the dumbbells, the composition to be tested was applied to a Teflon mold and the composition was allowed to crosslink for 14 days under standard conditions (23° C. and 50% relative humidity).

[0280] The principle of the measurement consists in stretching a standard test specimen in a tensile testing machine whose movable jaws move at a constant speed equal to 500 mm / min and recording:

[0281] - elongation at break (expressed in %) is the elongation of the test specimen corresponding to the elongation observed at break,

[0282] - 100% modulus (in MPa) is the tensile stress corresponding to 100% elongation of the test specimen,

[0283] - the modulus of elasticity (expressed in MPa) is the slope of the tangent line at the origin of the curve plotting tensile stress as a function of the elongation of the test specimen, and

[0284] - Tensile strength (in MPa) is the tensile stress at which the test specimen breaks.

[0285] Repeat the measurement on 5 test specimens and calculate the corresponding average value of the results obtained.

[0286] Shear strength was measured according to the following method:

[0287] Two rectangular aluminum plates were used with the following dimensions: 100 mm x 25 mm x 2 mm. After cleaning both plates with acetone, a rectangular adhesive bonding area with dimensions of 12.5 mm x 25 mm was defined at the end of each plate using tape.

[0288] On the adhesive bonding area of ​​the first substrate thus produced, the silyl-modified polymer composition was applied in an amount corresponding to a thickness of 2 mm. Next, the adhesive bonding area of ​​the second substrate was superimposed on the area thus coated, so as to obtain an assembly in which the free ends of the two substrates were aligned on either side of the two areas joined by the sealant.

[0289] The obtained test specimen assembly was held by a jig in a room with a controlled atmosphere at 23° C. and 50% relative humidity for 14 days to perform crosslinking of the composition.

[0290] The two free ends of the specimen are stretched with the aid of a tensile testing machine at a constant speed equal to 50 mm / min until the assembly breaks, and the stress applied thereto is recorded.

[0291] The measurement was repeated for 3 component specimens and the average value of the shear stress at break (referred to as shear strength) obtained was calculated.

[0292] Note also whether the failure was cohesive (failure within the composition) or adhesive (failure at the composition / board interface).

[0293] Example 2 : Effect of incorporation of carbon black as a function of its OAN

[0294] Comparative composition 1a was prepared according to the method described below by mixing the ingredients in the proportions shown in Table 1 below in several steps in a stirred reactor.

[0295] The ingredients of step 1 were mixed at ambient temperature (about 23° C.), at atmospheric pressure and at a low stirring speed (sufficient for homogenization).

[0296] Next, the ingredients of Step 2 were added to the reactor used for Step 1 and mixed first at atmospheric pressure and at a high agitation speed (to shear and mix the solids), then the reactor was placed under vacuum (16 kPa), the temperature was raised to 75-80°C and mixing was carried out for 10 to 30 minutes.

[0297] Finally, add the ingredients from step 3 under vacuum and mix at a low stirring speed (enough for homogenization).

[0298] Table 1

[0299]

[0300] Compositions 1b to 1e were prepared according to the same method as comparative composition 1a and had the same composition, except:

[0301] - for comparative composition 1b, 2% by weight of CALOFORT SV14 were replaced by 2% by weight of PRINTEX 25, relative to the total weight of the composition;

[0302] - for comparative composition 1c, 5% by weight of CALOFORT SV14 are replaced by 5% by weight of PRINTEX 25, relative to the total weight of the composition;

[0303] - for composition 1d according to the invention, 2% by weight of CALOFORT SV14 are replaced by 2% by weight of ELFTEX S5100, relative to the total weight of the composition;

[0304] For the composition 1e according to the invention, 5% by weight of CALOFORT SV14 are replaced by 5% by weight of ELFTEXS5100, relative to the total weight of the composition.

[0305] For example, comparative composition 1b has the same composition as 1a except that it includes 43.5 wt % CALOFORTSV14 and 2 wt % PRINTEX 25.

[0306] Carbon black (PRINTEX 25 or ELFTEX S5100) was also added during step 2 of the process.

[0307] The mechanical properties of composition Nos. 1 to 4 (measured according to Example 1) are summarized in Table 2 below.

[0308] Table 2

[0309]

[0310] By comparing the results obtained for compositions 1a and 1b, it can be concluded that the introduction of PRINTEX 25 does not significantly increase the tensile strength of the composition and is able to slightly improve the elongation at break (increase of 11%).

[0311] Furthermore, when a large amount of PRINTEX 25 is introduced, this does not significantly increase the tensile strength of the composition and has no effect on its elongation at break (compare the results obtained for compositions 1b and 1c).

[0312] On the other hand, the tensile strength of composition 1d (2% ELFTEX S5100) is 21% higher than that of composition 1a, and its elongation at break is improved by 28%, while the tensile strength of composition 1e (5% ELFTEX S5100) is 38% higher than that of composition 1a, and its elongation at break is improved by 22%.

[0313] Thus, the introduction of ELFTEX S5100 (carbon black with an OAN of 108 ml / 100 g) into a silyl-modified polymer composition significantly improves the tensile strength and elongation at break of the composition, an effect that is not obtained when PRINTEX 25 (carbon black with an OAN of 45 ml / 100 g) is introduced.

[0314] Example 3 : Comparative composition 2a not including any rheological agent

[0315] The various ingredients of comparative composition 2a were mixed in several steps in a stirred reactor in the proportions shown in Table 3 below according to the method described below.

[0316] The ingredients of step 1 are mixed at ambient temperature (about 23° C.), at atmospheric pressure and at a low stirring speed (sufficient for homogenization).

[0317] Next, the ingredients of Step 2 were added to the reactor used for Step 1 and mixed first at atmospheric pressure and at a high agitation speed (to shear and mix the solids), then the reactor was placed under vacuum (16 kPa), the temperature was raised to 75-80°C, and mixing was performed for 10 to 30 minutes.

[0318] Finally, add the ingredients from step 3 under vacuum and mix at a low stirring speed (enough for homogenization).

[0319] Table 3

[0320]

[0321] Example 4 : Comparative composition 2b not including any rheological agent

[0322] Comparative composition 2b is similar to comparative composition 2a, except that a plasticizer (Hexamoll DINCH).

[0323] The various ingredients of comparative composition 2b were mixed in several steps in a stirred reactor according to the method described in Example 3 in the proportions shown in Table 4 below.

[0324] Table 4

[0325]

[0326] Example 5 : Composition 2c according to the invention

[0327] Composition 2c according to the invention is similar to comparative composition 2b, except that a rheological agent (THIXATROL AS 8053).

[0328] The various ingredients of comparative composition 2c were mixed in a stirred reactor in several steps according to the method described in Example 3 in the proportions shown in Table 5 below, except that the temperature in step 2 was increased to 50-55° C. (corresponding to THIXATROL AS 8053 activation temperature) instead of 75-80°C.

[0329] Table 5

[0330]

[0331] Example 6 : Composition 2d according to the invention

[0332] Composition 2d is similar to composition 2c, except that another rheological agent (CRAYVALLAC SLX).

[0333] The various ingredients of composition 2d were mixed in several steps in a stirred reactor according to the method described in Example 3 in the proportions shown in Table 6 below.

[0334] Table 6

[0335]

[0336] Example 7 : Mechanical properties of compositions 2a to 2d

[0337] The mechanical properties of compositions 2a to 2d (measured according to Example 1) are summarized in Table 7 below.

[0338] Table 7

[0339]

[0340] The addition of rheological agents to compositions 2c and 2d according to the invention makes it possible to significantly improve the elongation at break and the tensile strength of the compositions.

[0341] In fact, the tensile strength (THIXATROL AS 8053) has an 8% higher tensile strength than composition 2b and a 23% improvement in elongation at break, while composition 2d (CRAYVALLAC The tensile strength of composition 2a) is 11% higher than that of composition 2b, and its elongation at break is improved by 25%.

[0342] Compositions 2c and 2d according to the invention also have the advantage of exhibiting a 100% cohesive failure mode.

Claims

1. Composition, include: - Silyl-modified polymers, - carbon black having an oil absorption number (OAN) of at least 80 ml / 100 g, and - Rheological agents.

2. A composition as claimed in claim 1, wherein the silyl-modified polymer comprises at least one, preferably at least two, alkoxysilane groups of formula (I): ， in: -R 4 represents a linear or branched alkyl group comprising 1 to 4 carbon atoms, and when p is equal to 2, R 4 The groups are the same or different, -R 5 represents a linear or branched alkyl group comprising 1 to 4 carbon atoms, and when p is equal to 0 or 1, R 5 The groups are the same or different, two OR 5 The groups may be inserted into the same ring, and - p is an integer equal to 0, 1 or 2, preferably equal to 0 or 1.

3. The composition of claim 1 or 2, wherein the silyl-modified polymer has formula (II), (III) or (IV): ， in: -R 4 , R 5 and p have the same meanings as in the above formula (I), - P represents a saturated or unsaturated polymeric radical having a linear or branched open chain or comprising one or more optional aromatic rings, 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, -R 1 represents a saturated or unsaturated divalent hydrocarbon radical comprising 5 to 15 carbon atoms, having a linear or branched open chain, or comprising one or more optional aromatic rings, -R 3 represents a linear or branched divalent alkylene group comprising 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, - X represents a member selected from –NH–, –NR 7 – or –S–, -R 7 represents a linear or branched alkyl group comprising 1 to 20 carbon atoms and which may also comprise one or more heteroatoms, - 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.

4. The composition of claim 3, wherein the silyl-modified polymer has formula (II'), (II''), (III') or (IV'): ， in: -R 1 , R 3 , R 4 , R 5 ,X,R 7 and p have the same meanings as in formulae (II), (III) and (IV), -R 2 represents a linear or branched, saturated or unsaturated divalent hydrocarbon radical, which optionally comprises one or more heteroatoms such as oxygen, nitrogen, sulfur, silicon, and optionally comprises one or more ionic groups, - n is an integer, preferably n is such that the number average molar mass of the silyl-modified 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.

5. A composition as claimed in claim 4, wherein the silyl-modified polymer is a polymer of formula (III'), and in: -R 2 represents an isopropylidene group, -R 4 and R 5 each represents a methyl group, and - p is equal to 1.

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

7. The composition of any one of claims 1 to 6, wherein the rheological agent is one or more thixotropic agents.

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

9. The composition of any one of claims 1 to 8, further comprising at least one adhesion promoter selected from the group consisting of amino-, mercapto- and epoxy-alkoxysilanes, preferably aminoalkoxysilanes, more preferably aminotrialkoxysilanes, even more preferably aminotrimethoxysilanes.

10. The composition as claimed in claim 9, wherein the at least one adhesion promoter is a mixture of at least two adhesion promoters, preferably two adhesion promoters.

11. The composition of claim 10, wherein the at least one adhesion promoter is a mixture of two adhesion promoters selected from the group consisting of 4-amino-3,3-dimethylbutyltrimethoxysilane, (3-aminopropyl)trimethoxysilane and n-butyl-3-aminopropyltrimethoxysilane.

12. A method for assembling two substrates by adhesive bonding, include: - applying the composition according to any one of claims 1 to 11 to at least one of the two substrates to be assembled; Then - physically bringing the two substrates into contact.

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

14. Use of the composition according to any one of claims 1 to 11 for adhesive bonding and sealing, in particular in the field of building construction, transport, such as road, sea, rail or air transport, and shipbuilding, preferably in the field of road, sea, rail or air transport, in particular for attaching glass panes, such as windscreens or windows, to the body of a vehicle, preferably for replacing the windscreen of a vehicle.

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