Composition comprising a serialized polymer

Abstract

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

Description

Technical Field

[0001] The present invention relates to compositions comprising a silyl-modified polymer and to their use, in particular for adhesive bonding and sealing.

Background Art

[0002] There are various polymer-based compositions on the market, which can be used in many fields, particularly as sealants. A sealant enables the assembly (or bonding or attachment) of two substrates that can be selected from the most diverse materials and can also be used as a sealing joint. The sealant provides the thus obtained assembly with advantageous mechanical properties such as robustness, elasticity, and / or flexibility, as well as fluid tightness.

[0003] For example, polymer-based compositions can be used as sealants in the construction, shipbuilding, or transportation sectors (e.g., road, marine, railway, or aerospace transportation).

[0004] For certain applications, particularly when attaching a glass plate (e.g., a windshield or a window) to the body of a vehicle, it is necessary for the polymer-based composition to have specific mechanical properties, particularly high tensile strength and high elongation at break. Specifically, it is essential that the composition does not break while being subjected to impact.

[0005] Compositions commercially available for windshield replacement are usually compositions based on isocyanate-terminated polyurethanes and generally have high tensile strength and high elongation at break. When the composition is used in the manufacture of an assembly, the reaction of water in the air or water originating from the substrates to be assembled with the isocyanate-reactive groups is called a crosslinking reaction. When this reaction is completed after a period called the crosslinking time, a solid three-dimensional network can be formed that helps to impart the desired mechanical properties to the thus formed adhesive joint.

[0006] Compositions based on alkoxysilane-terminated polymers (also called silyl-modified polymers) have the advantage of not containing isocyanates. Therefore, these compositions are alternatives to compositions based on isocyanate-terminated polyurethanes, which is preferable from the perspective of toxicity.

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

[0008] However, it is difficult to obtain compositions based on silyl-modified polymers, especially sealants, that have both high tensile strength and high elongation at break. Specifically, compositions containing 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 containing silyl-modified polymers that have improved tensile strength and elongation at break characteristics, especially similar to those of compositions based on isocyanate-terminated polyurethanes.

Summary of the Invention

[0010] The present invention relates to - a silyl-modified polymer, - carbon black having an oil absorption number (OAN) of at least 80 ml / 100 g, and - a rheology agent and relates to a composition containing the same.

[0011] Another subject of the present invention is - coating at least one of two substrates to be assembled with the composition according to the present invention as defined above; and then - actually bonding the two substrates together and is a process for assembling two substrates by adhesive bonding, which includes the above steps.

[0012] The present invention also relates to an article, preferably a vehicle, obtained according to the assembly process defined above.

[0013] The present invention also relates to a vehicle comprising a composition as defined herein, said composition being in contact simultaneously with a first substrate and a second substrate of said vehicle.

[0014] Furthermore, the present invention relates to the use of a sealant, in particular of the composition according to the invention as a sealing joint.

[0015] Finally, the present invention relates to the use of the composition according to the invention for adhesive bonding and sealing.

[0016] Surprisingly, it has been found that adding a combination of a rheology agent and carbon black with a high OAN to a silyl-modified polymer composition can significantly improve both the tensile strength and the elongation at break of the composition.

[0017] Therefore, the composition according to the invention is particularly advantageous for attaching a glass plate (for example, a windshield or a window) to the vehicle body, in particular for replacing the windshield of a vehicle.

Embodiments for Carrying Out the Invention

[0018] Therefore, the present invention is - a silyl-modified polymer, - carbon black having an oil absorption (OAN) of at least 80 ml / 100 g, and - a rheology agent relates to a composition comprising.

[0019] Cyrillic-modified polymer The "silyl-modified polymer" is understood to mean a polymer containing at least one alkoxysilane group. Preferably, the silyl-modified polymer contains at least one alkoxysilane group located at the end of the polymer.

[0020] Silyl-modified polymers are generally in the form of a more or less viscous liquid. Advantageously, the silyl-modified polymer has a viscosity of 10 to 200 Pa·s, preferably 20 to 175 Pa·s, more preferably 30 to 150 Pa·s, and even more preferably 45 to 125 Pa·s at 23°C.

[0021] 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).

[0022] In the context of the present invention, numerical ranges are understood to mean the limiting values included. For example, the range "between 0% and 25%" specifically includes the values 0% and 25%.

[0023] Advantageously, the silyl-modified polymer has an alkoxysilane group of formula (I): TIFF2025521089000001.tif8170[wherein, - R 4 represents a linear or branched alkyl radical containing 1 to 4 carbon atoms, and when p is equal to 2, R 4 radicals are the same or different, - R 5 represents a linear or branched alkyl radical containing 1 to 4 carbon atoms, and when p is equal to 0 or 1, R 5 radicals are the same or different, and two OR 5 groups may be inserted into the same ring, and - p is an integer equal to 0, 1, or 2, preferably an integer equal to 0 or 1] and contains at least one, preferably at least two.

[0024] Preferably, the alkoxysilane group of the silyl-modified polymer is of formula (I) with the following: - R 4 and R 5 each represents a methyl radical, and - p is equal to 0 or 1.

[0025] Advantageously, the silyl-modified polymer has a number-average molar mass between 500 g / mol and 70,000 g / mol, preferably between 4,000 g / mol and 60,000 g / mol, more preferably between 10,000 g / mol and 50,000 g / mol.

[0026] The molar mass of the polymer can be measured by methods well known to those skilled in the art, such as NMR or size-exclusion chromatography using polystyrene standards.

[0027] Advantageously, the silyl-modified polymer is of formula (II), (III), or (IV): TIFF2025521089000002.tif71170[wherein, - R 4 、R 5 and p have the same meaning as in formula (I) above, - P represents a saturated or unsaturated polymer radical having a linear or branched open chain, or containing one or more optional aromatic rings, optionally containing one or more heteroatoms such as oxygen, nitrogen, sulfur, and / or silicon, preferably oxygen and / or nitrogen, and optionally containing one or more ionic groups, - R 1 represents a saturated or unsaturated divalent hydrocarbon radical containing 5 to 15 carbon atoms, having a linear or branched open chain, or containing one or more optional aromatic rings, - R 3 represents a linear or branched divalent alkylene radical containing 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, - X represents a divalent radical selected from -NH-, -NR 7 -, or -S-, - R 7 represents a linear or branched alkyl radical containing 1 to 20 carbon atoms and optionally containing one or more heteroatoms, - f is an integer in the range of 1 to 6, preferably 2 to 5, more preferably 2 to 4, and even more preferably 2 to 3.

[0028] Advantageously, the silyl-modified polymer is of formula (II), (III), or (IV), where P represents a polymer radical selected from polyethers, polycarbonates, polyesters, polyolefins, polyacrylates, polyether polyurethanes, polyester polyurethanes, polyolefin polyurethanes, polyacrylate polyurethanes, polycarbonate polyurethanes, block polyether / polyester polyurethanes, and polysiloxanes, preferably a polymer radical selected from polyethers, polyurethanes, and mixtures thereof, and more preferably a polyether.

[0029] Preferably, the silyl-modified polymer is of the following formula (II’), (II’’), (III’), or (IV’): TIFF2025521089000003.tif88170[where - R 1 、R 3 、R 4 、R 5 、X、R 7 、and p have the same meaning as in formulas (II), (III), and (IV), - R 2 represents a linear or branched saturated or unsaturated divalent hydrocarbon radical optionally containing one or more heteroatoms such as oxygen, nitrogen, sulfur, silicon, etc., and optionally containing one or more ionic groups, - n is an integer, and 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 4000 g / mol and 60,000 g / mol, and even more preferably between 10,000 g / mol and 50,000 g / mol.

[0030] In the silyl-modified polymers of formulas (II’), (II’’), (III’), and (IV’) defined above, R 2When the radical contains one or more heteroatoms, the heteroatom does not exist at the chain end. In other words, the divalent R bonded to the adjacent oxygen atoms of the silyl-modified polymer 2 The free valences of the radicals each originate from a carbon atom. Therefore, R 2 The main chain of the radical is terminated by carbon atoms at both ends, and the carbon atoms have free valences.

[0031] According to one embodiment, the silyl-modified polymer is a polyol selected from polyether polyols, polyester polyols, polycarbonate polyols, polyacrylate polyols, polysiloxane polyols, polyolefin polyols, and mixtures thereof, preferably a diol selected from polyether diols, polyester diols, polycarbonate diols, polyacrylate diols, polysiloxane diols, polyolefin diols, and mixtures thereof, more preferably obtained from a polyether diol. In the case of the polymers of formulas (II’), (II’’), (III’), and (IV’) described above, such a diol has the formula HO-R 2 -OH or H-[O-R 2 n -OH, wherein R 2 has the same meaning as in formulas (II’), (II’’), (III’), and (IV’).

[0032] In particular, in the silyl-modified polymer of formula (IV’) defined above, the R 2 radicals may be the same or different, that is, the silyl-modified polymer of formula (IV’) can be a silyl-modified copolyurethane obtained from the same or different HO-R 2 -OH diols.

[0033] According to one embodiment, when the silyl-modified polymer is of formula (II’) or (IV’), the R 2 radical can be selected from the following divalent radicals showing two free valences: - Derivatives of polypropylene glycol:​ TIFF2025521089000004.tif25170- Derivatives of polyester diols: TIFF2025521089000005.tif23170- Derivatives of polybutadiene diol: TIFF2025521089000006.tif27170- Derivatives of polyacrylate diol: TIFF2025521089000007.tif31170- Derivatives of polysiloxane diol: TIFF2025521089000008.tif26170[In the formula, - q, R 2 represents an integer such that the number average molar mass of the radical is in the range of 100 g / mol to 48,600 g / mol, preferably 300 g / mol to 18,600 g / mol, and more preferably 500 g / mol to 12,600 g / mol, - r and s are R 2 represents a zero or non-zero integer such that the number average molar mass of the radicals 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, and it is understood that the sum r+s is non-zero, - 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 having 1 to 8 carbon atoms, - Q 2 represents a linear or branched divalent alkylene radical, preferably having 2 to 36 carbon atoms, more preferably having 1 to 8 carbon atoms, - Q 3 , Q 4 , Q 5 , Q 6 , Q 7 and Q 8 represent, independently of each other, a hydrogen atom or an alkyl, alkenyl, or aromatic radical, preferably containing from 1 to 12 carbon atoms, preferably from 2 to 12 carbon atoms, more preferably from 2 to 8 carbon atoms.

[0034] According to a specific embodiment, when the silyl-modified polymer is of formula (IV’), the silyl-modified polymer can be obtained from different HO-R 2 -OH diols, where one R 2 radical can be selected from the above divalent radicals (derivatives of polypropylene glycol, polyester diol, polybutadiene diol, polyacrylate diol, polysiloxane diol), and one R 2 radical is an ionic divalent radical of the following formula: TIFF2025521089000009.tif33170[wherein, - x and y may be the same or different and are integers in the range of 1 to 8, - z is an integer in the range of 0 to 8, - R 0 represents a hydrogen atom or an alkyl radical containing 1 to 18 carbon atoms, and - R, R’, and R’’ may be the same or different and each represents a saturated, unsaturated, or aromatic hydrocarbon radical optionally containing a heteroatom selected from N, O, and S; further, R, R’, and R’’ are such that the tertiary amine of formula N(R)(R’)(R’’) is a linear, branched, or cyclic amine, or a polyamine having a number average molar mass Mn in the range of 59 to 6000 g / mol and a pKa greater than 8].

[0035] According to one embodiment, R 1 is selected from the following divalent radicals that exhibit two free valences: a) A divalent radical derived from isophorone diisocyanate (IPDI): TIFF2025521089000010.tif25170b) A divalent radical derived from dicyclohexylmethane diisocyanate (H12MDI): TIFF2025521089000011.tif15170c) Divalent radicals derived from the 2,4- and 2,6-isomers of toluene diisocyanate (TDI): TIFF2025521089000012.tif36170d) Divalent radicals derived from the 4,4'- and 2,4'-isomers of diphenylmethane diisocyanate (MDI): TIFF2025521089000013.tif23170e) Divalent radicals derived from hexamethylene diisocyanate (HDI): -(CH2)6- f) Divalent radicals derived from m-xylylene diisocyanate (m-XDI): TIFF2025521089000014.tif25170

[0036] According to a preferred embodiment, the silyl-modified polymer is of formula (II'') or (III'), preferably (III'), and R 2 The radical is preferably a straight-chain or branched divalent alkylene radical containing 2 to 4 carbon atoms, more preferably a straight-chain or branched divalent alkylene radical containing 3 carbon atoms, and even more preferably an isopropylene radical (of the formula -CH2-CH(CH3)-).

[0037] According to a particularly preferred embodiment, the silyl-modified polymer is a polymer of formula (III'), wherein - R 2 represents an isopropylene radical, - R 4 and each of R 5 represents a methyl radical, and - p is equal to 1.

[0038] The polymers of formula (II), (II'), and (II'') can be obtained, for example, according to the processes described in the specifications of European Patent Application Publication No. 2336208 and International Publication No. 2009 / 106699. Examples of polymers corresponding to formula (II) include: - Geniosil® STP-E10 (available from Wacker Chemie): a dimethoxy-type of formula (I) having a number-average molar mass of 8889 g / mol, where p is equal to 1 and R 4and R 5 A polyether of formula (II'') containing two groups of (where R 3 represents a methyl group); - Geniosil® STP - E30 (available from Wacker Chemie): A dimethoxy - type of formula (I) (p is equal to 1, R 4 and R 5 A polyether of formula (II'') containing two groups of (where R 3 represents a methyl group); - Desmoseal® S XP 2636 (available from Bayer): A polyurethane of trimethoxy - type of formula (I) (p is equal to 0, R 5 A polyurethane containing two groups of (where R 3 represents an n - propylene group).

[0039] The polymer of formula (III) or (III') can be obtained, for example, by hydrosilylation of polyether diallyl ether by the process described in European Patent Application Publication No. 1829928. Examples of the polymer corresponding to formula (III) include: - MS SAX® 350 (available from Kaneka): A polymer corresponding to a polyether of dimethoxy - type of formula (I) (p is equal to 1, R 4 and R 5 represent methyl groups) and having a number - average molar mass in the range of 14000 - 16000 g / mol; - MS SAX® 260 (available from Kaneka): A polymer corresponding to a polyether of dimethoxy - type of formula (I) (p is equal to 1, R 4 and R 5 represent methyl groups) and having a number - average molar mass in the range of 16000 - 18000 g / mol (where R 3 represents an ethyl group); - A polymer corresponding to a polyether containing two groups of the dimethoxy type of formula (I) (p is equal to 1, and R 4 represents a methyl group) having a number average molecular weight of 21,000 to 23,000 g / mol; MS S303H (available from Kaneka); - A polymer corresponding to a polyether containing two groups of the dimethoxy type of formula (I) (p is equal to 1, and R 4 and R 5 represent a methyl group) having a number average molar mass of about 41 kg / mol, where R 2 represents an isopropylene radical; MS SAX® 725 (available from Kaneka).

[0040] The polymer of formula (IV) or (IV') can be obtained, for example, by the reaction of (one or more) polyols with one or more diisocyanates, followed by reaction with an aminosilane or a mercaptosilane. The process for preparing the polymer of formula (IV) or (IV') is described, for example, in European Patent Application Publication No. 2583988. Those skilled in the art will know how to adapt the manufacturing process described herein when using different types of polyols. Examples of polymers corresponding to formula (IV) include: - SPUR® 1050MM (available from Momentive): A polyurethane having a number average molar mass of 16,393 g / mol and containing two groups of the trimethoxy type of formula (I) (p is equal to 0, and R 5 represents a methyl group), where R 3 represents an n-propyl group; - SPUR® Y-19116 (available from Momentive): A polyurethane having a number average molar mass in the range of 15,000 to 17,000 g / mol and containing two groups of the trimethoxy type of formula (I) (p is equal to 0, and R 5 represents a methyl group), where R 3 represents an n-propyl group).

[0041] The content of the silyl-modified polymer in the composition according to the present invention can be in the range of 5% by weight to 60% by weight, preferably 10% by weight to 55% by weight, more preferably 20% by weight to 50% by weight, still more preferably 30% by weight to 45% by weight, and particularly 35% by weight to 40% by weight, based on the total weight of the composition.

[0042] Carbon black The carbon black in the composition of the present invention has an oil absorption amount (OAN) of at least 80 ml / 100 g.

[0043] The OAN of carbon black corresponds to the volume in ml of dibutyl phthalate (DBP) oil absorbed by 100 g of carbon black.

[0044] The OAN can be measured using DBP oil, for example, in accordance with the ASTM D-2414 method.

[0045] Unless otherwise specified, the standards mentioned throughout this application are the standards effective as of the filing date.

[0046] The carbon black used in the present invention is generally called "structured" carbon black and is generally different from the carbon black used as a pigment, particularly because of its high OAN.

[0047] Specifically, the carbon black used as a pigment is of lower quality than the carbon black used in the present invention and has a lower OAN.

[0048] An example of the carbon black used as a pigment is PRINTEX® 25 (sold by Orion) having an OAN of 45 ml / 100 g.

[0049] Examples of carbon blacks that can be used in the present invention include ELFTEX® S7100 and ELFTEX® S5100 (sold by CABOT), which have OANs of about 117 ml / 100 g and 108 ml / 100 g, respectively.

[0050] The term "about X" is intended to mean plus or minus 10% of the value of X.

[0051] Preferably, the OAN of the carbon black is at least 90 ml / 100 g, more preferably at least 100 ml / 100 g, and even more preferably at least 110 ml / 100 g.

[0052] Advantageously, the carbon black content in the composition according to the present invention is at least 2% by weight, preferably 3% to 20% by weight, more preferably 5% to 18% by weight, and even more preferably 6% to 15% by weight, for example 6%, based on the total weight of the composition.

[0053] Rheology agent The rheology agent enables adjustment of the rheological properties of the composition according to the present invention.

[0054] As an example, any rheology agent commonly used in the field of sealant compositions can be mentioned.

[0055] Advantageously, the rheology agent is one or more thixotropic agents, which are, for example, solid at 23°C and / or have a viscosity exceeding 200 mPa·s at 23°C in accordance with ISO standard 12058-1, and are preferably solid at 23°C. Thixotropic agents generally affect the thixotropy of the composition. Thixotropy is the property that when a certain force (e.g., shear at a certain stress) is applied, the viscosity of a specific composition decreases, and after the stress disappears, the viscosity returns to the initial state after an appropriate period. The greater the force, the lower the viscosity.

[0056] In particular, one or more rheology agents selected from the following are used: - PVC plastisols corresponding to a suspension of PVC in a plasticizer miscible with PVC and obtained in situ by heating to a temperature in the range of 60 °C to 80 °C. These plastisols may in particular be those described in the publication Polyurethane Sealants, Robert M. Evans, ISBN 087762-998-6; - Fumed silica, such as HDK® N20 sold by Wacker; - Urea derivatives resulting from the reaction of an aromatic diisocyanate monomer such as 4,4’-MDI with an aliphatic amine such as butylamine. The preparation of such urea derivatives is described in particular in French Patent Application No. 1591172; - Waxes derived from castor oil, such as THIXCIN® R available from Elementis; - Amide waxes, preferably micronized amide waxes such as CRAYVALLAC® SLX, CRAYVALLAC® SLW, or CRAYVALLAC® SUPER sold by Arkema, or THIXATROL® AS8053 or THIXATROL® MAX (EC number: 432-430-3) available from Elementis, or RHEOBYK 7503 sold by BYK.

[0057] These rheology agents are thixotropic agents.

[0058] The term "wax derived from castor oil" is understood to mean a wax obtained from castor oil, particularly hydrogenated castor oil. The wax derived from castor oil is solid at 23 °C.

[0059] 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 can be obtained from (one or more) fatty acids (such as ricinoleic acid) and (one or more) (di)amines. Amide waxes are solid at 23°C.

[0060] Preferably, the rheology agent is an amide wax and / or a wax derived from castor oil, more preferably an amide wax.

[0061] Amide waxes are preferably micronized, i.e., have an average particle size of less than 1 mm. Advantageously, amide waxes have an average particle size of less than 500 μm, preferably less than 100 μm, more preferably less than 10 μm.

[0062] 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 by laser diffraction using a laser particle size analyzer, in particular a MALVERN device (for example, in accordance with the NF ISO standard 13320).

[0063] Amide wax type rheology agents can be heat activatable, i.e., during the preparation of the composition according to the invention, a temperature above room temperature (23°C) may be required to activate them (in particular, to activate their rheological properties, in particular thixotropic properties).

[0064] The activation temperature depends on the rheology agent.

[0065] 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.

[0066] Advantageously, the content of the rheology agent in the composition according to the present invention is in the range of 0.2% to 20% by weight, preferably 1% to 10% by weight, and more preferably 1% to 5% by weight based on the total weight of the composition.

[0067] Adhesion promoter The composition according to the present invention may also contain at least one adhesion promoter.

[0068] Advantageously, the adhesion promoter is selected from amino silanes, mercapto silanes, and epoxy-alkoxysilanes, preferably aminoalkoxysilanes, more preferably aminotrialkoxysilanes, and even more preferably aminotrimethoxysilanes.

[0069] As an example of epoxyalkoxysilane, (3-glycidyloxypropyl)trimethoxysilane (also known as GLYMO) can be mentioned.

[0070] Advantageously, aminotrimethoxysilane is formed from the group consisting of 4-amino-3,3-dimethylbutyltrimethoxysilane (e.g., Silquest A-Link 600 sold by Momentive), (3-aminopropyl)trimethoxysilane (e.g., Dynasylan® AMMO sold by Evonik), and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (e.g., Dynasylan® DAMO or DAMO-T sold by Evonik). Preferably, aminotrimethoxysilane is formed from the group consisting of 4-amino-3,3-dimethylbutyltrimethoxysilane and (3-aminopropyl)trimethoxysilane.

[0071] Advantageously, the composition according to the present invention contains at least one adhesion promoter.

[0072] According to a preferred embodiment, at least one adhesion promoter is a mixture of at least two adhesion promoters, preferably a mixture of two adhesion promoters.

[0073] 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 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.

[0074] According to the preferred embodiment in which the adhesion promoter is a mixture of two adhesion promoters, the weight ratio of (the first adhesion promoter) / (the second adhesion promoter) is advantageously between 0.25 and 4, preferably between 0.5 and 2, more preferably between 0.7 and 1.5, and for example equal to 1.

[0075] The content of the (one or more) adhesion promoter(s) in the composition according to the present invention can be in the range of 0.2% by weight to 5% by weight, preferably 0.5% by weight to 3% by weight, more preferably 1.0% by weight to 2.0% by weight, based on the total weight of the composition.

[0076] Filler Advantageously, the composition according to the present invention further comprises a filler.

[0077] Preferably, the filler is selected from mineral fillers, organic fillers, and mixtures thereof, more preferably mineral fillers.

[0078] Advantageously, the mineral filler is formed from the group consisting of clay, quartz, hollow mineral microspheres, and carbonate fillers.

[0079] Among the hollow mineral microspheres, in particular, hollow glass microspheres, more specifically those made from sodium calcium borosilicate or aluminosilicate, can be mentioned.

[0080] Preferably, the mineral filler is formed from the group consisting of carbonate fillers.

[0081] According to a preferred embodiment, the composition according to the invention further comprises a carbonate filler, advantageously selected from alkali carbonates 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, and even more preferably precipitated calcium carbonate coated with a fatty acid.

[0082] Coating calcium carbonate with a fatty acid makes it possible to impart overall or partial hydrophobicity to the calcium carbonate particles. Furthermore, the coating of the fatty acid acts as a hydrophobic coating and can prevent the calcium carbonate from absorbing and inactivating the components of the composition. The hydrophobic coating of calcium carbonate can account for 0.1% to 3.5% by weight based on the total weight of calcium carbonate.

[0083] Preferably, the fatty acid for coating calcium carbonate contains or consists of more than 50% by weight of stearic acid based on the total weight of the fatty acid.

[0084] Examples of non-precipitated calcium carbonate coated with a fatty acid include OMYACARB 2T-AV or OMYA BLH (sold by OMYA), or CALATEM C16T (sold by Provencale).

[0085] Examples of precipitated calcium carbonate coated with a fatty acid include HAKUENKA® CCR-S10 (sold by OMYA) or CALOFORT® (sold by Specialty Minerals).

[0086] Advantageously, the organic filler is formed from the group consisting of polyvinyl chloride (PVC), polyolefin, rubber, ethylene / vinyl acetate (EVA), expandable or non-expandable hollow thermoplastic polymer microspheres (such as hollow vinylidene chloride / acrylonitrile microspheres), and aramid fibers (such as Kevlar®), and is preferably formed from PVC.

[0087] Advantageously, the average particle size of the filler is between 10 nm and 400 μm, preferably between 20 nm and 100 μm, more preferably between 30 nm and 1 μm, and even more preferably between 40 nm and 300 nm.

[0088] 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 by laser diffraction using a laser particle size analyzer, particularly a MALVERN device, (for example, in accordance with the NF ISO standard 13320).

[0089] Advantageously, the filler content ranges from 10 wt% to 80 wt%, preferably from 20 wt% to 60 wt%, more preferably from 30 wt% to 50 wt%, and even more preferably from 35 wt% to 40 wt% based on the total weight of the composition.

[0090] Crosslinking catalyst The composition according to the invention may also contain a crosslinking catalyst.

[0091] The catalyst can be any catalyst known to those skilled in the art for the condensation of silanols. Examples of catalysts include the following: - Organic derivatives of titanium, such as titanium acetylacetonate (such as TYZOR® AA75 sold by Dorf Ketal), etc. - Aluminum, such as aluminum chelates (such as K-KAT® 5218 sold by King Industries), etc. - Amines, such as 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), etc., - Zinc carboxylate and DBU-based catalysts (e.g., K-KAT® 670 sold by King Industries), - Tin-based catalysts, such as compounds derived from dioctyltin or dibutyltin; in particular, dioctyltin oxide, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dicarboxylate, dioctyltin diacetylacetonate (DBTDAA), dibutyltin dilaurate (DBTDL), dibutyltin diacetate, or dibutyltin oxide, preferably dioctyltin oxide or dibutyltin oxide. For example, NEOSTANN® S-1 (sold by KANEKA), or TIB KAT® 425 or TIB KAT® 423 (sold by TIB CHEMICALS) can be mentioned, - Guanidine derivatives, such as 1-(o-tolyl)biguanide (CAS No.: 93-69-6), such as Rhenocure 1000 C (sold by RheinChemie Additives), etc.

[0092] Preferably, the crosslinking catalyst is a tin-based catalyst, preferably selected from compounds derived from dioctyltin and dibutyltin, more preferably selected from dioctyltin oxide or dibutyltin oxide.

[0093] The content of the crosslinking catalyst in the composition according to the present invention can be in the range of 0.01% by weight to 5% by weight, preferably 0.02% by weight to 2% by weight, more preferably 0.05% by weight to 1% by weight, and even more preferably 0.1% by weight to 0.8% by weight, based on the total weight of the composition.

[0094] The composition according to the invention may also further comprise a crosslinking co-catalyst. Advantageously, the crosslinking co-catalyst is an organic polyester derived from silicic acid, i.e., an organic compound derived from silicic acid containing at least two alkoxysilane functionalities. For example, tetraethoxysilane (e.g., WACKER® TES 28 or TES 40 WN) or 1,2-bis(triethoxysilyl)ethane (e.g., Dynasylan® BTSE) may be mentioned.

[0095] The total weight of the crosslinking co-catalyst in the composition according to the invention may range from 0.01% by weight to 5% by weight, preferably from 0.05% by weight to 2% by weight, more preferably from 0.1% by weight to 1% by weight, based on the total weight of the composition.

[0096] Other additives The composition according to the invention may further comprise at least one additive selected from plasticizers, water absorbents, solvents, UV stabilizers, and mixtures thereof.

[0097] Advantageously, the composition according to the invention comprises a mixture of additives selected from plasticizers, water absorbents, solvents, and UV stabilizers (or antioxidants).

[0098] The total content of additives in the composition according to the invention may range from 0.5% by weight to 30% by weight, preferably from 5% by weight to 25% by weight, more preferably from 10% by weight to 20% by weight, based on the total weight of the composition.

[0099] Advantageously, the composition according to the invention contains a plasticizer. The plasticizer is different from a rheology agent because the properties of the composition containing the plasticizer will be the same whether stress (such as shear) is applied or not, while the properties of the composition containing a rheology agent will be different when stress is applied. The plasticizer can be used to adjust the viscosity (like a solvent).

[0100] The plasticizer can be any plasticizer commonly used in the field of sealant compositions.

[0101] Preferably, the plasticizer is selected from the following: - Diisodecyl phthalate (e.g., PALATINOL® DIDP sold by BASF), - Diisononyl phthalate (DINP) (e.g., PALATINOL® N sold by BASF), - Alkyl sulfonic acid esters of phenol (e.g., MESAMOLL® sold by LANXESS), - Diisononyl 1,2 - cyclohexanedicarboxylate (e.g., HEXAMOLL DINCH® sold by BASF), and - Pentaerythritol tetravalerate (e.g., PEVALEN™ sold by PERSTORP).

[0102] More preferably, the plasticizer is diisononyl 1,2 - cyclohexanedicarboxylate.

[0103] Advantageously, the plasticizer content ranges from 2 wt% to 25 wt%, preferably 5 wt% to 20 wt%, more preferably 7 wt% to 15 wt% based on the total weight of the composition.

[0104] The composition according to the present invention may also contain a solvent in an amount of 0 wt% to 5 wt% based on the total weight of the composition, preferably a solvent that is volatile at normal temperature (a temperature of about 23 °C). The volatile solvent can be selected from volatile alcohols such as ethanol or isopropanol at normal temperature. The volatile solvent can, for example, reduce the viscosity of the composition and facilitate the application of the composition. Due to the volatile nature of the solvent, the joint obtained after curing the composition no longer contains the solvent. Therefore, the solvent does not, for example, adversely affect the hardness of the joint.

[0105] Advantageously, the composition according to the invention comprises a moisture absorbent of up to 3.5% by weight, based on the total weight of the composition, which can be selected from vinyltrimethoxysilane (e.g., Dynasylan® VTMO sold by Evonik), propyltrimethoxysilane (e.g., Dynasylan® PTMO sold by Evonik), vinyltriethoxysilane (VTEO), alkoxyarylsilane (e.g., GENIOSIL® XL 70 sold by Wacker), p-toluenesulfonyl isocyanate (PTSI), and calcium oxide.

[0106] Preferably, the moisture absorbent is selected from vinyltrimethoxysilane, vinyltriethoxysilane, and alkoxyarylsilane, and more preferably vinyltrimethoxysilane.

[0107] Advantageously, the composition according to the invention comprises one or more UV stabilizers (or antioxidants) of up to 1% by weight, based on the total weight of the composition. UV stabilizers are usually introduced to protect the composition from degradation caused by reactions with oxygen, which is prone to form upon the action of heat or light. These compounds can include antioxidants that can trap free radicals.

[0108] Advantageously, the (one or more) UV stabilizer(s) (or antioxidant) is selected from hindered benzotriazoles, benzophenones, phenols, and amines, such as bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (CAS No.: 41556-26-7), methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate (CAS No.: 82919-37-7), octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate, 4,4'-bis(α,α-dimethylbenzyl) diphenylamine, and mixtures thereof. Examples include products such as IRGANOX 1076, TINUVIN® 292, TINUVIN® 765, or TINUVIN® 770 DF sold by BASF, RIASORB UV-123 sold by RIANLON, AddWorks® IBC 760 sold by Clariant, and OKABEST CLX 50 sold by OKA.

[0109] Preferably, the (one or more) UV stabilizer(s) (or antioxidant) is selected from hindered phenols and amines, such as bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate, 4,4'-bis(α,α-dimethylbenzyl) diphenylamine, and mixtures thereof.

[0110] According to one embodiment, the UV stabilizer (or antioxidant) is a mixture of bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate, and 4,4′-bis(α,α-dimethylbenzyl) diphenylamine.

[0111] Other features of the composition according to the present invention According to one embodiment, the composition according to the invention comprises: - a silyl-modified polymer in an amount of 5% to 60% by weight, based on the total weight of the composition, - at least 3% by weight of carbon black having an OAN of at least 80 ml / 100 g, based on the total weight of the composition, - a rheology agent (preferably a thixotropic agent) in an amount of 0.2% to 20% by weight, based on the total weight of the composition, - one or more adhesion promoters in an amount of 0.2% to 5% by weight, based on the total weight of the composition, - a filler in an amount of 10% to 80% by weight, based on the total weight of the composition, - a crosslinking catalyst in an amount of 0.01% to 5% by weight, based on the total weight of the composition, - optionally, a crosslinking co-catalyst in an amount of 0.01% to 5% by weight, based on the total weight of the composition, and - one or more additives selected from plasticizers, moisture absorbents, solvents, and UV stabilizers in an amount of 0.5% to 30% by weight, based on the total weight of the composition.

[0112] Preferably, the composition according to the invention consists essentially of the above-mentioned components. The term "consisting essentially of" is understood to mean that the composition according to the invention contains, based on the total weight of the composition, less than 5% by weight, preferably less than 2% by weight, and even more preferably less than 1% by weight of components other than the above-mentioned components.

[0113] The components of this embodiment and their specific contents are as described above, including the embodiment.

[0114] According to one specific embodiment, the composition according to the invention comprises: - a silyl-modified polymer in an amount of 35% to 40% by weight, based on the total weight of the composition, preferably a polymer of formula (III'), - Carbon black in an amount of 6% to 15% by weight based on the total weight of the composition, having an OAN of at least 80 ml / 100 g, preferably at least 110 ml / 100 g, - A rheology agent in an amount of 1% to 5% by weight based on the total weight of the composition, which is an amide wax, - An adhesion promoter in an amount of 1.0% to 2.0% by weight based on the total weight of the composition, selected from aminotrimethoxysilane, - A filler in an amount of 35% to 40% by weight based on the total weight of the composition, which is precipitated calcium carbonate coated with a fatty acid, - A crosslinking catalyst in an amount of 0.1% to 0.8% by weight based on the total weight of the composition, which is a tin-based catalyst, - Optionally, a crosslinking co-catalyst in an amount of 0.1% to 1% by weight based on the total weight of the composition, which is an organic polyester derived from silicic acid, and - One or more additives in an amount of 10% to 20% by weight based on the total weight of the composition, selected from plasticizers, moisture absorbents, solvents, and UV stabilizers.

[0115] Preferably, the composition according to the present invention consists essentially of the above-mentioned components.

[0116] The components of this embodiment and their specific contents are as described above, including the embodiment.

[0117] Advantageously, the composition according to the present invention has a tensile strength (often abbreviated as TS) of 3.5 MPa or more, preferably 4 MPa or more, more preferably 4.2 MPa or more, and even more preferably 4.4 MPa or more.

[0118] Advantageously, the composition according to the present invention has an elongation at break of more than 210%, preferably 300% or more, more preferably 400% or more, and even more preferably 500% or more.

[0119] According to a preferred embodiment, the composition according to the invention has a tensile strength of 3.5 MPa or more and an elongation at break of more than 210%, preferably a tensile strength of 4 MPa or more and an elongation at break of 300% or more, more preferably a tensile strength of 4.2 MPa or more and an elongation at break of 400% or more, and even more preferably a tensile strength of 4.4 MPa or more and an elongation at break of 500% or more.

[0120] Those skilled in the art know how to determine the tensile strength and elongation at break of a composition. For example, the tensile strength and elongation at break can preferably be measured at a constant speed equal to 500 mm / min, in accordance with ISO standard 37 (December 2005).

[0121] In particular, the tensile strength and elongation at break can be measured as described in Example 1 below.

[0122] Preparation of the composition according to the present invention The composition according to the invention can be prepared by simply mixing its components.

[0123] According to a preferred embodiment, the composition according to the invention is prepared according to the following process: - 1) The silyl-modified polymer is mixed in a suitable container with liquid additives such as a plasticizer, a solvent, a water absorbent, and a UV stabilizer (or antioxidant), preferably at a temperature between 18°C and 28°C and at atmospheric pressure, and then - 2) Carbon black having at least 80 ml / 100 g of OAN, and any other solid components such as solid additives such as a rheology agent, a filler, and a UV stabilizer (or antioxidant) are dispersed in the aforementioned liquid mixture for the time required to obtain a homogeneous mixture, and then - 3) Any other remaining liquid components such as an adhesion promoter and a catalyst are added and the medium is homogenized.

[0124] Preferably, step 2) is carried out at a pressure below atmospheric pressure, more preferably at a pressure below 50 kPa, and even more preferably at a pressure below 20 kPa.

[0125] Preferably, step 2) is carried out at a temperature above 30 °C, more preferably above 40 °C. When the composition according to the invention contains a thermoactivatable rheology agent, the mixing of the solid components is advantageously carried out at the temperature at which the rheology agent is activated.

[0126] Preferably, step 3) is carried out at a pressure and temperature substantially equal to those used in step 2).

[0127] An example of preparing the composition according to the invention is described in Example 2.

[0128] Other subjects of the present invention Another subject of the invention is - coating at least one of the two substrates to be assembled with the composition according to the invention as defined above; then - actually bonding the two substrates A process for assembling two substrates by adhesive bonding, comprising.

[0129] The substrates involved are very diverse and are preferably selected from concrete, metals such as aluminum and / or steel, and glass.

[0130] According to a preferred embodiment, one of the substrates is steel (for example, part of a vehicle body), and the other substrate is glass (for example, a glass plate such as a windshield or a window).

[0131] The invention also relates to an article, preferably a vehicle, obtained according to the assembly process defined above.

[0132] The invention also relates to a vehicle comprising the composition as defined herein, said composition being in contact with the first and second substrates of said vehicle simultaneously, preferably in contact with part of the vehicle body and a glass plate such as a windshield.

[0133] Furthermore, the present invention relates to the use of a sealant, in particular of the composition according to the invention as a sealing joint.

[0134] Finally, the present invention relates to the use of the composition according to the invention for adhesively bonding and sealing, in particular for attaching a glass plate (for example, a windshield or a window) to the body of a vehicle, preferably for replacing the windshield of a vehicle, in particular in the fields of construction, transport, for example, road, sea, rail, or aerospace transport, and shipbuilding, preferably in the fields of road, sea, rail or aerospace transport.

[0135] All of the above-described embodiments can be combined with each other. In particular, the various above components of the composition, in particular the preferred embodiments of the composition, can be combined with each other.

[0136] The following examples are given only for the purpose of illustrating the present invention and should not be construed as limiting the scope of the present invention.

Examples

[0137] Example 1 : Components and Measuring Methods Components used The following components were used: - MS POLYMER (trademark) S303H sold by KANEKA: 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; - MS POLYMER (trademark) SAX 725 sold by KANEKA: dimethoxysilane-terminated poly(propylene oxide) having a weight-average molar mass Mw of about 51 kg / mol, a number-average molar mass of about 41 kg / mol, and a viscosity of 87 Pa·s; - DYNASYLAN (registered trademark) VTMO sold by Evonik: vinyltrimethoxysilane (CAS number: 2768-02-7), a moisture absorbent; - DYNASYLAN® AMMO sold by Evonik: (3-aminopropyl)trimethoxysilane (CAS No.: 13822-56-5), an adhesion promoter; - CALOFORT® SV14 sold by Specialty Minerals: Precipitated calcium carbonate coated with fatty acids, having an average particle size of 70 nm; - OMYACARB 2T-AV sold by OMYA: Calcium carbonate (also known as GCC, short for ground calcium carbonate), having a d50 particle size of 2.7 μm and a moisture content of 0.2% or less based on the total weight of OMYACARB 2T-AV; - HAKUENKA® CCR-S10 sold by OMYA: Precipitated calcium carbonate coated with fatty acids, having an average particle size of 80 nm; - RIASORB UV-123 sold by RIANLON: Bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate (CAS No.: 129757-67-1), a hindered amine light stabilizer (HALS); - TINUVIN 770 DF sold by BASF: Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (CAS No.: 52829-07-9), a hindered amine light stabilizer (HALS); - PRINTEX® 25 sold by Orion: Carbon black having an OAN of 45 ml / 100 g measured in accordance with ASTM D-2414 method; - ELFTEX® S5100 sold by CABOT: Carbon black having an OAN of 108 ml / 100 g measured in accordance with ASTM D-2414 method; - ELFTEX® S7100 sold by CABOT: Carbon black having an OAN of 117 ± 6 ml / 100 g measured in accordance with ASTM D-2414 method; - SILQUEST A-link 600 sold by Momentive: 4-amino-3,3-dimethylbutyltrimethoxysilane (CAS No.: 157923-74-5), a non-yellowing adhesion promoter; - NEOSTANN S-1 sold by KANEKA: Reaction product of silicic acid (H4SiO4), tetraethyl ester, and bis(acetyloxy)dibutylstannane (CAS No.: 93925-43-0), a crosslinking catalyst; - TIB KAT 425 sold by TIB CHEMICALS: TIB KAT 232 (dioctyltin oxide) / silane mixture, a crosslinking catalyst; - THIXATROL® AS 8053 sold by Elementis: A micronized amide wax rheology agent with an average diameter of less than 5 μm; - CRAYVALLAC® SLX sold by Arkema: A micronized amide wax rheology agent (particle size less than 5 μm); - Hexamoll® DINCH sold by BASF: Diisononyl 1,2-cyclohexanedicarboxylate, a plasticizer.

[0138] Measurement method Tensile strength, elongation at break, elastic modulus, and 100% elastic modulus were measured in accordance with ISO standard 37 (December 2005) at a constant speed equal to 500 mm / min.

[0139] In particular, the following conditions were applied:

[0140] A standard test piece in the shape of a type 1 dumbbell shown in ISO international standard 37 (December 2005) was 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.

[0141] To prepare the dumbbell, the composition to be tested was applied to a Teflon mold, and the composition was left to crosslink by standing for 14 days under standard conditions (23 °C and 50% relative humidity).

[0142] The principle of measurement consists of stretching a standard test piece with a tensile testing machine in which the movable jaw moves at a constant speed equal to 500 mm / min, and recording the following: - The elongation at break (expressed in % units) is the elongation of the test piece corresponding to the elongation observed at break, - The 100% modulus (in MPa units) is the tensile stress corresponding to a 100% elongation of the test piece, - The modulus (expressed in MPa units) is the slope of the tangent at the origin of the curve plotting the tensile stress as a function of the elongation of the test piece, - The tensile strength (in MPa units) is the tensile stress at which the test piece breaks.

[0143] The measurement is repeated for five test pieces, and the corresponding average of the results obtained is calculated.

[0144] The shear strength was measured according to the following method:

[0145] Two rectangular aluminum plates with the following dimensions: 100 mm × 25 mm × 2 mm are used. After washing the two plates with acetone, adhesive tape is used to demarcate a rectangular bonding area with dimensions of 12.5 mm × 25 mm at the ends of each plate.

[0146] To the bonding area of the first substrate plate thus produced, a silyl-modified polymer composition is applied in an amount corresponding to a thickness of 2 mm. Next, the bonding area of the second substrate plate is overlaid on the area thus coated, and an assembly is obtained in which the free ends of the two substrate plates are aligned on both sides of two regions bonded with a sealant.

[0147] The test piece assembly obtained is held with clips in a room with a controlled atmosphere at 23 °C and a relative humidity of 50% for 14 days for crosslinking of the composition.

[0148] The two free ends of the test piece are pulled using a tensile testing machine at a constant speed equal to 50 mm / min until the assembly breaks, and the applied stress is recorded.

[0149] Measurements are repeated for three assembly test pieces, and the average of the shear stresses (referred to as shear strengths) at break obtained is calculated.

[0150] Record whether the failure is cohesive (failure within the composition) or adhesive (failure at the composition / plate interface).

[0151] Example 2 :Effect of Incorporation of Carbon Black as a Function of OAN Comparative composition 1a is prepared by mixing the components in several steps according to the process described below in a stirred reactor at the ratios shown in Table 1 below.

[0152] Mix the components of step 1 at room temperature (about 23 °C), atmospheric pressure, and a low stirring speed (sufficient for homogenization).

[0153] Next, add the components of step 2 to the reactor used in step 1, first mix at atmospheric pressure and a high stirring speed (to shear and mix the solids), then place the reactor under reduced pressure (16 kPa), raise the temperature to 75 - 80 °C, and mix for 10 - 30 minutes.

[0154] Finally, add the components of step 3 under reduced pressure and mix at a low stirring speed (sufficient for homogenization). TIFF2025521089000015.tif69170

[0155] Compositions 1b - 1e are prepared according to the same process as comparative composition 1a and have the same composition except for the following: - In comparative composition 1b, 2 wt% of CALOFORT SV14 is replaced with 2 wt% of PRINTEX 25 based on the total weight of the composition; - In comparative composition 1c, 5 wt% of CALOFORT SV14 is replaced with 5 wt% of PRINTEX 25 based on the total weight of the composition; - In composition 1d according to the present invention, 2 wt% of CALOFORT SV14 is replaced with 2 wt% of ELFTEX S5100 based on the total weight of the composition; - In Composition 1e according to the present invention, 5% by weight of CALOFORT SV14 is replaced with 5% by weight of ELFTEX S5100 based on the total weight of the composition.

[0156] For example, Comparative Composition 1b has the same composition as Comparative Composition 1a, except that it contains 43.5% by weight of CALOFORT SV14 and 2% by weight of PRINTEX 25.

[0157] During Step 2 of the process, carbon black (PRINTEX 25 or ELFTEX S5100) is also added.

[0158] The mechanical properties (measured according to Example 1) of Composition Nos. 1 to 4 are summarized in Table 2 below. TIFF2025521089000016.tif38170

[0159] Comparing the results obtained for Compositions 1a and 1b, it can be concluded that incorporating PRINTEX 25 cannot significantly improve the tensile strength of the composition, and only a slight improvement (11% increase) in elongation at break is possible.

[0160] Furthermore, even when a larger amount of PRINTEX 25 is incorporated, it cannot significantly increase the tensile strength of the composition, nor does it affect the elongation at break (comparing the results obtained for Composition 1b and Composition 1c).

[0161] On the other hand, the tensile strength of Composition 1d (2% ELFTEX S5100) is 21% higher than that of Composition 1a, the elongation at break is improved by 28%, and the tensile strength of Composition 1e (5% ELFTEX S5100) is 38% higher than that of Composition 1a, and the elongation at break is improved by 22%.

[0162] Therefore, when ELFTEX S5100 (carbon black with 108 ml / 100 g OAN) is incorporated into the silyl-modified polymer composition, both the tensile strength and elongation at break of the composition are significantly improved, but this effect cannot be obtained when PRINTEX 25 (carbon black with 45 ml / 100 g OAN) is incorporated.

[0163] Example 3 : Comparative composition 2a without rheology agent The various components of Comparative Composition 2a are mixed in a stirred reactor at the ratios shown in Table 3 below in several steps according to the following process.

[0164] The components of Step 1 are mixed at room temperature (about 23 °C), atmospheric pressure, and a low stirring speed (sufficient for homogenization).

[0165] Next, the components of Step 2 are added to the reactor used in Step 1, first mixed at atmospheric pressure and a high stirring speed (to shear and mix the solids), then the reactor is placed under reduced pressure (16 kPa), the temperature is raised to 75 - 80 °C, and mixing is carried out for 10 - 30 minutes.

[0166] Finally, the components of Step 3 are added under reduced pressure and mixed at a low stirring speed (sufficient for homogenization). TIFF2025521089000017.tif68170

[0167] Example 4 : Comparative composition 2b without rheology agent Comparative Composition 2b is the same as Comparative Composition 2a, except that a plasticizer (Hexamoll (registered trademark) DINCH) is added.

[0168] The various components of Comparative Composition 2b are mixed in a stirred reactor at the ratios shown in Table 4 below in several steps according to the process described in Example 3. TIFF2025521089000018.tif76170

[0169] Example 5 : Composition 2c according to the present invention The composition 2c according to the present invention is the same as the comparative composition 2b, except that a rheology agent (THIXATROL® AS 8053) is added.

[0170] The various components of the composition 2c are mixed in several steps according to the process described in Example 3 in a stirring reactor at the ratios shown in Table 5 below, except that the temperature in Step 2 is raised to 50 - 55 °C (corresponding to the activation temperature of THIXATROL® AS 8053) instead of 75 - 80 °C. TIFF2025521089000019.tif74170

[0171] Example 6 : Composition 2d according to the present invention The composition 2d is the same as the composition 2c, except that a different rheology agent is used (CRAYVALLAC® SLX).

[0172] The various components of the composition 2d are mixed in several steps in a stirring reactor at the ratios shown in Table 6 below according to the process described in Example 3. TIFF2025521089000020.tif74170

[0173] Example 7 : Mechanical properties of compositions 2a - 2d The mechanical properties (measured according to Example 1) of the compositions 2a - 2d are summarized in Table 7 below. TIFF2025521089000021.tif56170

[0174] Adding a rheology agent to the compositions 2c and 2d according to the present invention can significantly improve both the elongation at break and the tensile strength of the compositions.

[0175] In fact, when compared with the comparative composition 2b that does not contain a rheology agent, the tensile strength of composition 2c (THIXATROL® AS 8053) is 8% higher than that of composition 2b, and the elongation at break is improved by 23%. On the other hand, the tensile strength of composition 2d (CRAYVALLAC® SLX) is 11% higher than that of composition 2b, and the elongation at break is improved by 25%.

[0176] The compositions 2c and 2d according to the present invention also have the advantage of showing a 100% cohesive failure pattern.

Claims

1. - A silyl-modified polymer, - Carbon black having an oil absorption amount (OAN) of at least 80 ml / 100 g, and - A rheology agent A composition comprising.

2. The silyl-modified polymer has at least one, preferably at least two, of formula (I): [Wherein, -R ４ represents a linear or branched alkyl radical containing 1 to 4 carbon atoms, and when p is equal to 2, the R ４ radicals are the same or different, -R ５ represents a linear or branched alkyl radical containing 1 to 4 carbon atoms, and when p is equal to 0 or 1, the R ５ radicals are the same or different, and two OR ５ groups may be inserted into the same ring, and - p is an integer equal to 0, 1, or 2, preferably an integer equal to 0 or 1] The composition according to claim 1, which contains an alkoxysilane group.

3. The silyl-modified polymer is of formula (II), (III), or (IV): [Wherein, -R ４ , R ５ , and p have the same meaning as in the above formula (I), - P may have a linear or branched open chain, or may contain one or more aromatic rings, and may contain one or more heteroatoms such as oxygen, nitrogen, sulfur, and / or silicon, preferably contains oxygen and / or nitrogen, and may contain one or more ionic groups, representing a saturated or unsaturated polymer radical, -R １ represents a saturated or unsaturated divalent hydrocarbon radical containing 5 to 15 carbon atoms, having a straight-chain or branched-chain open chain, or optionally containing one or more aromatic rings, -R ３ represents a linear or branched divalent alkylene radical containing 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, - X represents a divalent radical selected from -NH-, -NR ７ -, or -S-; -R ７ represents a linear or branched alkyl radical containing 1 to 20 carbon atoms and may also contain one or more heteroatoms, - f is an integer in the range of 1 to 6, preferably 2 to 5, more preferably 2 to 4, and even more preferably 2 to 3] The composition according to claim 1 or 2, which is one of these.

4. The silyl-modified polymer is of the following formula (II'), (II''), (III'), or (IV'): [Wherein, -R １ , R ３ , R ４ , R ５ , X, R ７ , and p have the same meanings as those in formulas (II), (III), and (IV), -R ２ represents a linear or branched, saturated or unsaturated divalent hydrocarbon radical which may contain one or more heteroatoms such as oxygen, nitrogen, sulfur, silicon, etc. and may contain one or more ionic groups, - n is an integer, preferably 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 4000 g / mol and 60,000 g / mol, and even more preferably between 10,000 g / mol and 50,000 g / mol] The composition according to claim 3, which is one of these.

5. The silyl-modified polymer is a polymer of formula (III'), wherein, -R ２ represents an isopropylene radical, -R ４ and R ５ each represents a methyl radical, and - p is equal to 1, The composition according to claim 4.

6. The carbon black content is at least 2% by weight, preferably 3% to 20% by weight, more preferably 5% to 8% by weight, and even more preferably 6% to 15% by weight, for example 6%, based on the total weight of the composition. The composition according to any one of claims 1 to 5.

7. The rheology agent is one or more thixotropic agents. The composition according to any one of claims 1 to 6.

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

9. The composition according to any one of claims 1 to 8, further comprising at least one adhesion promoter selected from amino silanes, mercapto silanes and epoxy-alkoxy silanes, preferably selected from amino alkoxy silanes, more preferably selected from amino trialkoxy silanes, and even more preferably selected from amino trimethoxy silane.

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

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

12. A method of assembling two substrates by adhesive bonding, comprising: - Coating the composition according to any one of claims 1 to 11 on at least one of the two substrates to be assembled; then, - Actually adhering the two substrates. A method comprising the above steps.

13. Use of the composition according to any one of claims 1 to 11 as a sealant, particularly for sealing joints.

14. Use for adhesive bonding and sealing of the composition according to any one of claims 1 to 11, particularly for attaching a glass plate (e.g., windshield or window) to a vehicle body, preferably for replacing the windshield of a vehicle, particularly in the fields of construction, transportation, e.g., road, marine, railway, or aerospace transportation, and shipbuilding, preferably in the fields of road, marine, railway or aerospace transportation.

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