Two-component composition based on silylated polymer

Abstract

The invention relates to a two-component composition comprising at least one first composition comprising a silylated polymer and a second composition, wherein one of the first and second compositions comprises at least one filler comprising a hydroxide salt, and the other of the first and second compositions comprises at least one acid. The invention also relates to the use of such a two-component composition as an adhesive and / or mastic in a battery, and to a method for crosslinking a two-component composition of this kind.

Description

[0001] Two-component composition based on silylated polymer

[0002] Field of invention

[0003] The present invention relates to two-component compositions based on silylated polymer which can be used in particular as adhesives and / or sealants, as well as the use of such compositions in batteries.

[0004] Technical background

[0005] There are various polymer-based compositions on the market that can be used in many areas, including as adhesives and / or sealants. Adhesives and sealants are used to assemble (or join or bond) two substrates that can be chosen from a wide variety of materials.

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

[0007] Compositions based on alkoxysilane-terminated polymers (also known as silylated polymers) have the advantage of being isocyanate-free. These compositions therefore constitute a preferred alternative from a toxicological point of view to compositions based on isocyanate-terminated polyurethanes, which are very often found on the adhesive market.

[0008] The crosslinking reaction of these silylated polymer-based compositions occurs, in the presence of moisture, by hydrolysis of the alkoxysilane groups carried by the polymer, then by their condensation to form a siloxane bond (-Si-O-Si-) which unites the polymer chains into a solid three-dimensional network.

[0009] However, in some applications, these compositions are used in closed assemblies, such as batteries. These closed assemblies do not allow enough air (and therefore moisture) to pass through for the crosslinking reaction of the silylated polymer to take place.

[0010] It is possible to use as an adhesive a two-component composition comprising on the one hand the silylated polymer to be crosslinked, and on the other hand water. The two components of the adhesive are often packaged separately in the two compartments of a dual cartridge. The distribution of the adhesive is then carried out at the time of application on the substrates to be assembled, by extrusion of the two components, for example using a dual cartridge gun, and following their homogeneous mixing obtained, for example, by attaching a static mixer to the dual cartridge. The reaction of the component comprising the silylated polymer with the component comprising water allows the crosslinking of the silylated polymer.

[0011] However, water is hydrophilic while the silylated polymer is hydrophobic. Thus, there is a problem of processability when mixing the components because it is difficult to mix the component comprising water with the component comprising the silylated polymer, the water generally being deposited on the mixer blades.

[0012] There is therefore a real need to provide a two-component silylated polymer composition having good processability, capable of crosslinking efficiently and quickly, and which can be used in so-called "blocked" systems, i.e. in systems comprising non-porous surfaces which do not allow air humidity to pass through.

[0013] Summary of the invention

[0014] The invention relates firstly to a two-component composition comprising at least: a first composition comprising a silylated polymer; and a second composition; in which: one of the compositions among the first and second compositions comprises at least one filler comprising a hydroxide salt, and the other of the compositions among the first and second compositions comprises at least one acid.

[0015] The invention also relates to the use of the two-component composition as described above as an adhesive and / or sealant in a battery, preferably a rechargeable battery.

[0016] The invention also relates to a method of crosslinking a two-component composition as described above, comprising contacting the first composition with the second composition.

[0017] The present invention makes it possible to meet the need expressed above. It provides more particularly a two-component composition based on silylated polymer which can be used as an adhesive and / or sealant, in particular in so-called "blocked" systems which allow little air humidity to pass through, and which can be crosslinked without adding (free) water to the composition, which allows a more homogeneous mixing of the components of the composition (avoiding the problems of poor miscibility of free water with the silylated polymer which can occur in water-based adhesives) and better processability of the composition during its use. In addition, the two-component composition according to the invention gives rise, after mixing its two components, to a composition having good crosslinking throughout the composition, good adhesion properties as well as good mechanical properties.

[0018] This is accomplished by incorporating, into one of the two components forming the two-component composition, a hydroxide salt and incorporating into the other component an acid. Without wishing to be bound by theory, the inventor believes that upon bringing the two components of the two-component composition into contact, an acid-base reaction occurs in which the H ions + from the acid react with the OH- ions from the hydroxide salt to form water. The water thus produced allows the hydrolysis of the alkoxysilane groups of the silylated polymers which can then, by condensation, form a three-dimensional network.

[0019] Very advantageously, the hydroxide salt can also act as a thermally conductive filler, giving the composition according to the invention a thermally conductive character. In these advantageous embodiments, the composition according to the invention has good thermal conductivity, which makes it possible, for example, when the composition is used for the manufacture of batteries, to improve the lifespan of said batteries.

[0020] Also advantageously, the hydroxide salt can also have the function of flame retardant, which makes it possible, for example, to limit the quantities of additives added to the composition.

[0021] Detailed description

[0022] The invention is now described in more detail and in a non-limiting manner in the following description.

[0023] Unless otherwise stated, all percentages given are by mass.

[0024] In this text, the quantities indicated for a given species may apply to this species according to all its definitions (as mentioned in this text), including the more restricted definitions.

[0025] Within the scope of the invention, the ranges of values ​​are understood to include the limits. For example, the range “between 0% and 25%” includes in particular the values ​​0% and 25%.

[0026] Unless otherwise indicated, the standards referred to in this text are those in force on the date of filing of the patent application. In this text, “approximately X” means a value between plus or minus 10% of the value of X.

[0027] According to a first aspect, the invention relates to a two-component composition comprising a first composition (also called first component in the present text) and a second composition (also called second component in the present text). The first composition comprises at least one silylated polymer. The two-component composition according to the invention also comprises at least one filler comprising a hydroxide salt and at least one acid. Very preferably, the at least one hydroxide salt is present in one of the first and second compositions of the two-component composition and the at least one acid is present in the other of the first and second compositions.

[0028] The at least one silylated polymer is present in the first composition. The second composition may also comprise at least one silylated polymer, identical to or different from that or those present in the first composition. However, preferably, only the first composition comprises the silylated polymer(s).

[0029] By "silylated polymer" is meant a polymer comprising at least one alkoxysilane group. Preferably, the silylated polymer comprises at least one alkoxysilane group at the end of the polymer. Preferably, the silylated polymer comprises at least two alkoxysilane groups, more preferably in the terminal position.

[0030] The silylated polymer is generally in the form of a more or less viscous liquid. Advantageously, the silylated polymer has a viscosity at 23°C ranging from 0.5 to 200 Pa.s, preferably from 5 to 120 Pa.s, more preferably from 15 to 80 Pa.s, even more preferably from 30 to 60 Pa.s. The viscosity of the silylated polymer can be measured using a Brookfield-type method at 23°C and 50% relative humidity (S7 needle).

[0031] Preferably, the silylated polymer has a main chain selected from a polyether main chain, a polyether-polyurethane main chain, a polyester main chain, a polyester-polyurethane main chain, a polyether-polyester-polyurethane main chain, a polyolefin main chain, a polyolefin-polyurethane main chain, a polyether-polyolefin-polyurethane main chain, a polyacrylate main chain, a polyether-polyacrylate main chain, a polycarbonate main chain, a polycarbonate-polyurethane main chain and a polysiloxane main chain. Advantageously, the silylated polymer comprises at least one, preferably at least two, alkoxysilane groups of formula (I):

[0032] -If(R 4 )p(OR 5 ) 3.p (|) in which:

[0033] - R 4represents a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, and when p is equal to 2, the radicals R 4 are the same or different,

[0034] - R 5 represents a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, and when p is equal to 0 or 1, the radicals R 5 are identical or different, two OR groups 5 which can be engaged in the same cycle, and

[0035] - p is an integer equal to 0, 1 or 2, preferably equal to 0 or 1.

[0036] Preferably, the silylated polymer has a number average molar mass of 500 g / mol to 70,000 g / mol, preferably of 1,000 g / mol to 60,000 g / mol, more preferably of 2,000 g / mol to 50,000 g / mol. The number average molar mass of the polymers can be measured by methods well known to those skilled in the art, in particular by size exclusion chromatography using polystyrene standards.

[0037] Advantageously, the silylated polymer comprises, or is, a silylated polymer of form in which:

[0038] - R 4 , R 5 and p have the same meaning as in formula (I) described above,

[0039] - P represents a saturated or unsaturated polymeric radical, with a linear or branched open chain, or comprising one or more optionally aromatic cycles, optionally comprising one or more heteroatoms, such as oxygen, nitrogen, sulfur and / or silicon, preferably oxygen and / or nitrogen,

[0040] - R 1 represents a divalent hydrocarbon radical comprising from 5 to 15 carbon atoms, saturated or unsaturated, with a linear or branched open chain, or comprising one or more optionally aromatic cycles,

[0041] - R 3 represents a linear or branched divalent alkylene radical comprising from 1 to 6 carbon atoms, preferably from 1 to 3 carbon atoms,

[0042] - X represents a divalent radical chosen from -NH-, -NR 7 - or -S-,

[0043] - R 7represents a linear or branched alkyl radical comprising from 1 to 20 carbon atoms and which may also comprise one or more heteroatoms,

[0044] - 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.

[0045] Advantageously, the silylated polymer comprises, or is, a silylated polymer of formula (II), (III) or (IV) with P representing a polymeric radical chosen from polyethers, polycarbonates, polyesters, polyolefins, polyacrylates, polyether polyurethanes, polyester polyurethanes, polyolefin polyurethanes, polyacrylate polyurethanes, polycarbonate polyurethanes, polyether / polyester block polyurethanes, polyether polyacrylates, and mixtures thereof, preferably chosen from polyethers, polyacrylates, polyether polyacrylates, polyurethanes and mixtures thereof, more preferably from polyethers, polyacrylates, polyether polyacrylates, and mixtures thereof.

[0046] In embodiments, the silylated polymer comprises, or is, a silylated polymer of formula (IT), (II”), (III') and / or (IV'):

[0047] (R 5 O)3.p(R 4 )pSi— R 3 - GOLD 2 -FO- R 2 GOLD3 - If(R 4 ) p (GOLD 5 ) 3.p i_ _i n

[0048] (III') in which:

[0049] - R 1 , R 3 , R 4 , R 5 , X, R 7 and p have the same meaning as in formulas (H), (III) and (IV),

[0050] - R 2 represents a saturated or unsaturated, linear or branched, divalent hydrocarbon radical optionally comprising one or more heteroatoms, such as oxygen, nitrogen, sulfur and / or silicon,

[0051] - n is an integer that can be equal to 0.

[0052] Preferably n is such that the number-average molar mass of the silylated polymer is between 500 g / mol and 70,000 g / mol, more preferably between 1,000 g / mol and 60,000 g / mol, even more preferably between 2,000 g / mol and 50,000 g / mol.

[0053] In the silylated polymers of formulas (IT), (II”), (III') or (IV') defined above, when the radical R 2 comprises one or more heteroatoms, said heteroatom(s) are not present at the end of the chain. In other words, the free valences of the divalent radical R 2 linked to the neighboring oxygen atoms of the silylated polymer, each come from a carbon atom. Thus, the main chain of the radical R 2 is terminated by a carbon atom at each of the two ends, said carbon atom then having a free valence.

[0054] The silylated polymers may be obtained from polyols chosen from polyether polyols, polyester polyols, polycarbonate polyols, polyacrylate polyols, polysiloxane polyols, polyolefin polyols and mixtures thereof, preferably from diols chosen from polyether diols, polyester diols, polycarbonate diols, polyacrylate diols, polysiloxane diols, polyolefin diols and mixtures thereof, more preferably from polyether diols, polyacrylate diols, and mixtures thereof. In the case of the polymers of formulae (IT), (II”), (III') or (IV') described above, such diols may be represented by the formula HO-R 2 -OH or H-[O- R 2 ] n -OH, in which R 2 has the same meaning as in formulas (IT), (II”), (III') or (IV').

[0055] When the silylated polymer is of formula (II') or (IV'), the radical R 2can be chosen from the following divalent radicals (whose formulas below show the two free valencies):

[0056] - derived from a polypropylene glycol:

[0057] - derived from a polyester diol:

[0058] - derivative of a polybutadiene diol:

[0059] - derivative of a polyacrylate diol:

[0060] - derived from a polysiloxane diol: in which:

[0061] - q represents an integer such as the molar mass in number of the radical R 2 is 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,

[0062] - r and s represent zero or a non-zero integer such that the number-average molar mass of the radical R 2is from 100 g / mol to 48600 g / mol, preferably from 300 g / mol to 18600 g / mol, more preferably from 500 g / mol to 12600 g / mol, it being understood that the sum r+s is different from zero,

[0063] - Q 1 represents a linear or branched, saturated or unsaturated, aromatic or aliphatic divalent alkylene radical, preferably having from 1 to 18 carbon atoms, more preferably from 1 to 8 carbon atoms,

[0064] - Q 2 represents a linear or branched divalent alkylene radical preferably having from 2 to 36 carbon atoms, more preferably from 1 to 8 carbon atoms, - Q 3 , Q 4 , Q 5 , Q 6 , Q 7 and Q 8 , represent, independently of one another, a hydrogen atom or an alkyl, alkenyl or aromatic radical, preferably having from 1 to 12 carbon atoms, preferably from 2 to 12 carbon atoms, more preferably from 2 to 8 carbon atoms.

[0065] In embodiments, R 1 is chosen from the following divalent radicals (whose formulas below show the two free valencies):

[0066] - the divalent radical derived from isophorone diisocyanate (I PDI):

[0067] - the divalent radical derived from dicyclohexylmethane diisocyanate (H12MDI):

[0068] - divalent radicals derived from the 2,4- and 2,6- isomers of toluene diisocyanate (TDI):

[0069] - divalent radicals derived from the 4,4'- and 2,4'- isomers of diphenylmethane diisocyanate (MDI):

[0070] - the divalent radical derived from hexamethylene diisocyanate (HDI): -(CH2)6-

[0071] - the divalent radical derived from m-xylylene diisocyanate (m-XDI):

[0072] In particular embodiments, the silylated polymer comprises, or is, a silylated polymer of formula (II”) or (III') (preferably with R 3 representing a linear or branched divalent alkylene radical comprising 1 to 3 carbon atoms), preferably (III'), and the radical R 2 preferentially represents:

[0073] - a linear or branched divalent alkylene radical comprising from 2 to 4 carbon atoms, more preferably a linear or branched divalent alkylene radical comprising 3 carbon atoms, and / or

[0074] - a divalent radical derived from one or more acrylate monomers, the e(s) being in particular of formula: in which Q 3 , Q 4 , Q 5 and Q 6 are as defined above.

[0075] The silylated polymer may advantageously comprise, or be, a polymer of formula (III') in which:

[0076] - R 2is as defined above, in particular the particular embodiments above,

[0077] - R 5 represents a methyl radical, and

[0078] - p is equal to 0.

[0079] The polymers of formula (II), (II') or (II”) can be obtained according to a process described for example in documents EP 2336208 and WO 2009 / 106699. Among the polymers corresponding to formula (II), mention may be made of:

[0080] - GENIOSIL® STP-E10 (available from WACKER-CHEMIE): polyether of formula (II”) comprising two groups of formula (I) of the dimethoxy type (p equal to 1 and R 4 and R 5 represent a methyl group), having a number-average molar mass of 8889 g / mol, and in which R 3 represents a methyl group;

[0081] - GENIOSIL® STP-E30 (available from WACKER-CHEMIE): polyether of formula (II”) comprising two groups of formula (I) of the dimethoxy type (p equal to 1 and R 4 and R 5 represent a methyl group), having a number-average molar mass of 14493 g / mol, and in which R 3 represents a methyl group;

[0082] - DESMOSEAL® S XP 2636 (available from BAYER): polyurethane comprising two groups of formula (I) of the trimethoxy type (p equal to 0 and R 5 represents a methyl group), having a number-average molar mass of 15038 g / mol, and in which R 3 represents an n-propylene group. The polymers of formula (III) or (III') can be obtained by hydrosilylation of polyether diallyl ether according to a process described for example in document EP 1829928. Among the polymers corresponding to formula (III), mention may be made of:

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

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

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

[0086] - the MS SAX® 520 polymer (available from KANEKA) corresponding to a polyether comprising groups of formula (I) of the trimethoxy type (p equal to 0 and R 5 represents a methyl group) and having a number-average molar mass ranging from 29000 to 31000 g / mol;

[0087] - the Kaneka Silyl™ MA490 polymer marketed by KANEKA, corresponding to a poly(propylene oxide) / polyacrylate with trimethoxysilane terminations.

[0088] The polymers of formula (IV) or (IV') may for example be obtained by reaction of polyol(s) with one or more diisocyanate(s) followed by a reaction with aminosilanes or mercaptosilanes. A process for preparing polymers of formula (IV) or (IV') is described for example in document EP 2583988, this process being able to be adapted in a conventional manner by a person skilled in the art in the case of the use of different types of polyols. Among the polymers corresponding to formula (IV), mention may be made of:

[0089] - SPUR+® 1050MM (available from MOMENTIVE): polyurethane comprising two groups of formula (I) of the trimethoxy type (p equal to 0 and R 5 represents a methyl group), having a number-average molar mass of 16393 g / mol, and in which R 3 represents an n-propyl group;

[0090] - SPUR+® Y-19116 (available from MOMENTIVE): polyurethane comprising two groups of formula (I) of the trimethoxy type (p equal to 0 and R 5 represents a methyl group), having a number-average molar mass ranging from 15000 to 17000 g / mol g / mol, and in which R 3 represents an n-propyl group.

[0091] Advantageously, the amount of silylated polymer in the first composition is from 3% to 40%, preferably from 5% to 35% by weight, more preferably from 10% to 30% by weight, more preferably from 14% to 28% by weight, even more preferably from 17% to 22% by weight, relative to the total weight of the first composition. In embodiments, the amount of silylated polymer is from 3 to 10% by weight, or from 10 to 12% by weight, or from 10 to 14% by weight, or from 14 to 16% by weight, or from 16 to 17% by weight, or from 17 to 18% by weight, or from 18 to 19% by weight, or from 19 to 20% by weight, or from 20 to 21% by weight, or from 21 to 22% by weight, or from 22 to 24% by weight, or from 24 to 26% by weight, or from 26 to 28% by weight, or from 28 to 30% by weight, or from 30 to 35% by weight, or from 35 to 40% by weight, relative to the total weight of the first composition.

[0092] Preferably, the second composition is free of silylated polymer. Alternatively, it may comprise an amount of silylated polymer of 0.5 to 5% by weight, or 5 to 10% by weight, or 10 to 15% by weight, or 15 to 20% by weight, or 20 to 25% by weight, or 25 to 30% by weight, or 30 to 35% by weight, or 35 to 40% by weight, relative to the total weight of the second composition.

[0093] Filler comprising a hydroxide salt

[0094] The two-component composition according to the invention comprises at least one filler comprising a hydroxide salt.

[0095] Advantageously, the filler comprising the hydroxide salt is included in the first composition. Alternatively, it may be included in the second composition. Preferably, only one of the first and second compositions comprises the at least one filler comprising a hydroxide salt.

[0096] If one of the first and second compositions comprises both a filler comprising a hydroxide salt and an acid, then said composition preferably does not comprise a silylated polymer.

[0097] Advantageously, this filler is thermally conductive. A thermally conductive filler is a filler that allows heat to be diffused thanks to its thermal conductivity value. In particular, the thermally conductive filler makes it possible to confer good thermal conductivity on the composition according to the invention (advantageously between 0.5 and 3 W / mK).

[0098] Preferably, this filler consists of a hydroxide salt. The filler comprising a hydroxide salt may have undergone a surface treatment, in particular a hydrophobic treatment. For example, the surface treatment may be carried out with an alkylalkoxysilane, in particular an alkyltrialkoxysilane such as an alkyltrimethoxysilane and / or an alkyltriethoxysilane. By "alkylalkoxysilane" is meant a silane comprising at least one alkoxy group and at least one alkyl group, linked to a silicon atom. Preferably, the filler comprising a hydroxide salt has undergone a hydrophobic surface treatment.

[0099] The filler comprising a hydroxide salt may comprise, or preferably is, a hydroxide salt selected from the group consisting of poor metal hydroxides, alkali earth hydroxides, alkali hydroxides, silver(l) hydroxide, iron hydroxides, nickel(ll) hydroxide, uranyl hydroxide, and mixtures thereof. Preferably, the filler comprising a hydroxide salt comprises, or preferably is, a hydroxide salt selected from the group consisting of poor metal hydroxides, alkaline earth hydroxides, and mixtures thereof.

[0100] As poor metal hydroxides which can be used in the invention, mention may be made of aluminium hydroxide (also called ATH or aluminium oxide trihydrate, of formula Al(OH)3), cadmium hydroxide (Cd(OH)2), lead(II) hydroxide (Pb(OH)2), zinc hydroxide (Zn(OH)2) and mixtures thereof.

[0101] As alkaline earth hydroxides which may be used in the invention, mention may be made of beryllium hydroxide (Be(OH)2), magnesium hydroxide (Mg(OH)2), calcium hydroxide (Ca(OH)2), strontium hydroxide (Sr(OH)2), barium hydroxide (Ba(OH)2) and mixtures thereof.

[0102] As alkali hydroxides usable in the invention, mention may be made of lithium hydroxide (LiOH), sodium hydroxide (NaOH), potassium hydroxide (KOH), rubidium hydroxide (RbOH), cesium hydroxide (CsOH) and mixtures thereof.

[0103] As iron hydroxides usable in the invention, mention may be made of iron(ll) hydroxide (Fe(OH)2), iron(lll) hydroxide (Fe(OH)3), iron(lll) oxyhydroxide (FeO(OH)) and mixtures thereof.

[0104] In advantageous embodiments, the filler comprising a hydroxide salt comprises, or preferably is, a hydroxide salt selected from the group consisting of aluminum hydroxide, calcium hydroxide, magnesium hydroxide, cadmium hydroxide, lead(II) hydroxide, zinc hydroxide, strontium hydroxide, barium hydroxide, beryllium hydroxide, silver(I) hydroxide, iron hydroxides, nickel(II) hydroxide and mixtures thereof. More preferably, the filler comprising a hydroxide salt comprises, or preferably is, a hydroxide salt selected from the group consisting of aluminum hydroxide, calcium hydroxide, magnesium hydroxide and mixtures thereof.

[0105] More preferably, the filler comprising a hydroxide salt comprises aluminum hydroxide. Even more preferably, the filler comprising a hydroxide salt is aluminum hydroxide.

[0106] Examples of thermally conductive fillers include metal hydroxides, in particular poor metal hydroxides, alkaline earth hydroxides, silver(l) hydroxide, iron hydroxides, nickel(ll) hydroxide and / or uranyl hydroxide, in particular aluminum hydroxide and / or magnesium hydroxide.

[0107] Advantageously, the filler comprising a hydroxide salt is also a flame retardant. When the filler comprising a hydroxide salt is aluminum hydroxide, this filler is a flame retardant.

[0108] The two-component composition according to the invention may advantageously comprise a quantity of filler comprising a hydroxide salt of 0.5 to 70% by weight, preferably of 1 to 65% by weight, more preferably of 10 to 60% by weight, more preferably of 20 to 55% by weight, even more preferably of 25 to 55% by weight, relative to the total weight of the two-component composition. In particular, the two-component composition may comprise a filler amount comprising a hydroxide salt of 0.5 to 5% by weight, or 5 to 10% by weight, or 10 to 15% by weight, or 15 to 20% by weight, or 20 to 25% by weight, or 25 to 30% by weight, or 30 to 35% by weight, or 35 to 40% by weight, or 40 to 45% by weight, or 45 to 50%, or 50 to 55% by weight, or 55 to 60% by weight, or 60 to 65% by weight, or 65 to 70% by weight, relative to the total weight of the two-component composition.

[0109] Advantageously, one of the first and second compositions (i.e. the first composition, or the second composition, preferably the first composition) comprises from 1 to 90% by weight of filler comprising a hydroxide salt, more preferably from 10 to 85% by weight, more preferably from 20 to 85% by weight, more preferably from 40 to 85% by weight, even more preferably from 50 to 80% by weight relative to the weight of said composition. In particular, the filler comprising a hydroxide salt may be present in said composition (i.e. in the first composition or in the second composition) in an amount of 1 to 10% by weight, or 10 to 20% by weight, or 20 to 30% by weight, or 30 to 40% by weight, or 40 to 50% by weight, or 50 to 55% by weight, or 55 to 60% by weight, or 60 to 65% by weight, or 65 to 70% by weight, or 70 to 75% by weight, or 75 to 80% by weight, or 80 to 90% by weight.

[0110] Acid

[0111] The two-component composition according to the invention comprises at least one acid.

[0112] Advantageously, the acid is present in the second composition. Alternatively, it may be included in the first composition. Very preferably, only one of the first and second compositions comprises the at least one acid. Even more preferably, the at least one filler comprising a hydroxide salt as described above is present in one of the first and second compositions and the at least one acid is present in the other of the first and second compositions. Even more preferably, the at least one filler comprising a hydroxide salt is present in the first composition and the at least one acid is present in the second composition.

[0113] If one of the first and second compositions comprises both a filler comprising a hydroxide salt and an acid, then said composition preferably does not comprise a silylated polymer.

[0114] The acid according to the invention may be a liquid acid or, advantageously, a solid acid (or a mixture thereof). The use of a solid acid has the advantage of facilitating mixing with the other ingredients of the composition, in particular when the latter contains a significant quantity of fillers.

[0115] Preferably the acid is a Brônsted acid, preferably having a pKa at 25°C less than or equal to 6, preferably less than or equal to 5.5, more preferably between -15 and 5.5, even more preferably between -3 and 5.0.

[0116] The pKa of an acid is equal to — log (Ka), where Ka is the acidity constant of the acid in water. For polyprotic acids, the lowest pKa associated with that polyprotic acid is targeted. For acid derivatives such as ammonium salts, their pKa is that of the ammonium ion (NH4 + ).

[0117] The pKa of acids are widely referenced in the scientific literature and are determined in a manner known to those skilled in the art (for example by potentiometric titration, by spectrophotometry or by nuclear magnetic resonance, generally by potentiometric titration for example described in engineering techniques (ref. K695 v1)). In the context of the present invention, the pKa is preferably that referenced in the scientific literature (for example in “Aqueous pKa compilation by Williams R (document compiled by Jencks WP, added to by Westheimer FH)” available on the internet: https: / / organicchemistrydata.org / hansreich / resources / pka / pka_data / pka-compilation-williams.pdf).

[0118] It is generally considered by those skilled in the art that Brônsted acids have a pKa at 25°C of less than 7. In contrast, acid derivatives such as ammonium salts have a pKa at 25°C of approximately 9. Thus, acid salts, in particular ammonium salts, are not Brônsted acids.

[0119] The acid according to the invention may have a molar mass of between 20 g / mol and 500 g / mol, preferably between 30 g / mol and 250 g / mol.

[0120] The acid according to the invention may be an inorganic acid or an organic acid (or a mixture thereof).

[0121] Examples of inorganic acids that can be used in the invention are phosphoric acid (of formula H3PO4), pyrophosphoric acid (of formula HO- P(=O)(OH)-OP(=O)(OH)-OH), polyphosphoric acids (of formula HO-[- P(=O)(OH)-O-] n-H with n greater than or equal to 3), phosphorous acid (of formula H3PO3), nitric acid HNO3, sulfuric acid H2SO4, hydrochloric acid HCl, hydrobromic acid HBr, and mixtures thereof.

[0122] As organic acids which can be used in the invention, mention may be made of:

[0123] - organic phosphates, corresponding to phosphoric acid esters, preferably organic phosphates of formula R'O- P(=O)(OR”)(OR'”) in which R', R”, R'” independently represent a hydrogen atom or a carbon chain (for example an alkyl or aryl group), at least one of R', R” and R'” being a hydrogen atom;

[0124] - phosphonic acids, preferably of formula RP(=O)(OH)2 in which R represents a carbon chain (for example an alkyl or aryl group) optionally comprising one or more heteroatoms; for example methylphosphonic acid;

[0125] - phosphonates, preferably of formula RP(=O)(OR')(OH) in which R represents a carbon chain (for example an alkyl or aryl group) optionally comprising one or more heteroatoms and R' represents a carbon chain (for example an alkyl or aryl group);

[0126] - sulfonic acids, preferably of formula RS(=O)2-OH in which R represents a carbon chain (for example an alkyl or aryl group) optionally comprising one or more heteroatoms; for example paratoluenesulfonic acid and methylsulfonic acid;

[0127] - carboxylic acids, preferably of formula RC(=O)OH in which R represents a carbon chain (for example an alkyl or aryl group) optionally comprising one or more heteroatoms; in particular aromatic carboxylic acids, more particularly benzoic acids, in which the benzene ring is optionally substituted by one or more additional groups (in addition to the carboxyl group), such as one or more alkyl, aromatic, OH and / or COOH groups; even more particularly salicylic acid and / or benzoic acid; and

[0128] - mixtures of these.

[0129] Preferably, the acid is selected from the group consisting of phosphoric acid, pyrophosphoric acid, polyphosphoric acids, organic phosphates, phosphonic acids, phosphonates, sulfonic acids, carboxylic acids and combinations thereof. More preferably, the acid is selected from the group consisting of phosphoric acid, pyrophosphoric acid, polyphosphoric acids, salicylic acid and mixtures thereof, even more preferably, the acid is phosphoric acid and / or salicylic acid.

[0130] The two-component composition according to the invention preferably comprises an amount of acid of 0.05 to 5% by weight, more preferably of 0.1 to 3% by weight, more preferably of 0.2 to 2% by weight, even more preferably of 0.2 to 1% by weight, in particular of 0.5 to 1% by weight, relative to the total weight of the two-component composition. For example, the two-component composition may comprise an amount of acid of 0.05 to 0.1% by weight, or 0.1 to 0.2% by weight, or 0.2 to 0.3% by weight, or 0.3 to 0.5% by weight, or 0.5 to 0.7% by weight, or 0.7 to 1% by weight, or 1 to 1.2% by weight, or 1.2 to 1.5% by weight, or 1.5 to 2% by weight, or 2 to 3% by weight, or 3 to 5% by weight, based on the total weight of the two-component composition.

[0131] Advantageously, one of the first and second compositions (i.e. the first composition, or the second composition, preferably the second composition) comprises from 0.1 to 10% by weight of acid, more preferably from 0.2 to 6% by weight, more preferably from 0.4 to 4% by weight, more preferably from 0.6 to 4% by weight, even more preferably from 1 to 2% by weight, relative to the weight of said composition. In particular, the acid may be present in the composition (i.e. in the first composition or in the second composition) in an amount of 0.1 to 0.3% by weight, or 0.3 to 0.5% by weight, or 0.5 to 0.7% by weight, or 0.7 to 1% by weight, or 1 to 1.2% by weight, or 1.2 to 1.5% by weight, or 1.5 to 1.7% by weight, or 1.7 to 2% by weight, or 2 to 2.5% by weight, or 2.5 to 3% by weight, or 3 to 4% by weight, or 4 to 5% by weight, or 5 to 10% by weight, relative to the total weight of said composition.

[0132] Thermally conductive filler Advantageously, the two-component composition comprises at least one additional filler, i.e. other than the filler comprising the hydroxide salt, this filler being thermally conductive (called “additional thermally conductive filler” in the present text). This at least one additional thermally conductive filler may be the only thermally conductive filler of the two-component composition (in the case where the filler comprising a hydroxide salt is not a thermally conductive filler) or, when the filler comprising a hydroxide salt is thermally conductive, may be an additional thermally conductive filler.

[0133] The additional thermally conductive filler may be included in the first composition, in the second composition or in each of the first and second compositions, preferably in the second composition or in each of the first and second compositions.

[0134] The presence of a thermally conductive filler makes it possible to confer good thermal conductivity on the two-component composition according to the invention. Thus, when the two-component composition comprises a thermally conductive filler (whether it is the filler comprising the hydroxide salt and / or the additional thermally conductive filler), the two-component composition is advantageously thermally conductive, that is to say, within the meaning of the present invention, that at least one of the first or second compositions has a thermal conductivity greater than or equal to 0.5 W / mK. The thermal conductivity of the first and second compositions can be determined by following the method of standard ASTM D5470. Preferably, the thermal conductivity of the first composition and / or the second composition is between 0.5 and 3 W / mK, more preferably between 1.0 and 2.0 W / mK, more preferably equal to approximately 1.5 W / mK.

[0135] The additional thermally conductive filler advantageously has a thermal conductivity greater than or equal to 3 W / mK, preferably greater than or equal to 5 W / mK, more preferably greater than or equal to 10 W / mK.

[0136] Advantageously, the additional thermally conductive filler is electrically insulating. By “electrically insulating filler” is meant in particular a filler having an electrical conductivity less than or equal to 0.1 S / m at 23°C, preferably less than or equal to 0.01 S / m at 23°C. The electrical conductivity can be measured according to ISO 787-14:2002.

[0137] The at least one additional thermally conductive filler may be chosen from aluminosilicates, alumina, aluminum nitride, boron nitride, zinc oxide, magnesium oxide and mixtures thereof, preferably from aluminosilicates, alumina, boron nitride, zinc oxide, magnesium oxide and mixtures thereof, more preferably from aluminosilicates, alumina and mixtures thereof, in particular alumina. The additional thermally conductive filler is preferably of natural origin (i.e. it is not synthetic).

[0138] The additional thermally conductive filler advantageously does not have a three-dimensional crystalline structure having pores of at least 3 Å in diameter.

[0139] Advantageously, at least one of the first and second compositions (the first composition and / or the second composition) comprises from 40% to 90% by weight, preferably from 50% to 87% by weight, more preferably from 55% to 85% by weight, even more preferably from 60% to 80% by weight, of additional thermally conductive filler, relative to the total weight of said composition; in particular from 40 to 50% by weight, or from 50 to 60% by weight, or from 60 to 70% by weight or from 70 to 80% by weight, or from 80 to 90% by weight, relative to the total weight of said composition.

[0140] In embodiments, one of the first and second compositions (the first composition or the second composition) comprises an amount of additional thermally conductive filler as described above, and the other of the first and second compositions comprises an amount of additional thermally conductive filler of 0 to 40% by weight, in particular of 0 to 30% by weight, more particularly of 0 to 20% by weight, relative to the total weight of said composition; for example of 0 to 5% by weight, or of 5 to 10% by weight, or of 10 to 15% by weight, or of 15 to 20% by weight, or of 20 to 30% by weight, or of 30 to 40% by weight.

[0141] Preferably, the two-component composition comprises from 10 to 80% by weight, more preferably from 15 to 60% by weight, more preferably from 20 to 40% by weight, of additional thermally conductive filler, relative to the total weight of the two-component composition. In embodiments, the two-component composition comprises from 10 to 15% by weight, or from 15 to 20% by weight, or from 20 to 25% by weight, or from 25 to 30% by weight, or from 30 to 35% by weight, or from 35 to 40% by weight, or from 40 to 50% by weight, or from 50 to 60% by weight, or from 60 to 70% by weight, or from 70 to 80% by weight, of additional thermally conductive filler, relative to the total weight of the two-component composition.

[0142] In embodiments, each of the first and second compositions comprises an additional thermally conductive filler. In other embodiments, only one of the first and second compositions comprises an additional thermally conductive filler.

[0143] Advantageously, the total content of thermally conductive filler(s) (including the filler comprising the hydroxide salt when the latter is thermally conductive) in the first composition is from 50% to 90% by weight relative to the total weight of the first composition, preferably from 55% to 87% by weight, more preferably from 60% to 85% by weight, even more preferably from 65% to 80% by weight.

[0144] Advantageously, the total content of thermally conductive filler(s) (including the filler comprising the hydroxide salt when the latter is thermally conductive) in the second composition is from 50% to 90% by weight relative to the total weight of the second composition, preferably from 55% to 87% by weight, more preferably from 60% to 85% by weight, even more preferably from 62% to 80% by weight.

[0145] Preferably, the total content of thermally conductive filler(s) (including the filler comprising the hydroxide salt when the latter is thermally conductive) in the two-component composition is from 50% to 90% by weight relative to the total weight of the two-component composition, preferably from 55% to 87% by weight, more preferably from 60% to 85% by weight, even more preferably from 65% to 80% by weight.

[0146] Preferably, the two-component composition comprises at least two thermally conductive fillers (including the filler comprising the hydroxide salt when the latter is thermally conductive).

[0147] In embodiments, the first composition and / or the second composition (e.g., each of them) comprises at least two thermally conductive fillers (including the filler comprising the hydroxide salt when the latter is thermally conductive). In embodiments, the first composition and / or the second composition (e.g., each of them) may comprise at least two additional thermally conductive fillers.

[0148] In embodiments, the two-component composition (in particular, the first composition and / or the second composition) comprises at least two additional thermally conductive fillers, the thermally conductive fillers in said composition having a different particle size. For example, the difference in volume median diameter d50 between two of the thermally conductive fillers may be between 5 pm and 25 pm, preferably between 10 pm and 20 pm. The volume median diameter d50 corresponds to the particle size at 50 ème percentile (in volume) of the cumulative distribution of particle sizes, and can be measured with a granulometer, in particular by laser diffraction, in particular on a MALVERN type device (for example according to standard NF ISO 13320).

[0149] Rheology agent

[0150] The two-component composition may comprise at least one rheology agent. The at least one rheology agent may be present in the first composition, or in the second composition, or in each of the first and second compositions. Preferably, the first composition comprises at least one rheology agent. More preferably, only the first composition comprises at least one rheology agent.

[0151] Preferably, the rheology agent comprises, or preferably is, a rheology agent chosen from:

[0152] - rheology agents (r1) chosen from amide waxes;

[0153] - rheology agents (r2) including:

[0154] ■ from 1% to 40% by weight of a bis-urea (a) obtained by reaction of a primary aliphatic amine with a diisocyanate of molar mass less than 500 g / mol, relative to the total weight of the rheology agent (r2), and

[0155] ■ from 60% to 99% by weight of a plasticizer (b) chosen from alkylphthalates, pentaerythritol tetravalerate, alkylsulfonic acid esters of phenol, diisononyl-1,2-cyclohexane dicarboxylate, 3,3'-[methylenebis(oxymethylene)]bis[heptane], dioctyl carbonate and mixtures thereof, relative to the total weight of the rheology agent (r2), said rheology agent (r2) being in the form of a suspension of solid particles of bis-urea (a) in a continuous phase of plasticizer (b);

[0156] - fumed silica;

[0157] - waxes derived from castor oil, such as for example THIXCIN® R marketed by ELEMENTIS;

[0158] - PVC plastisols, corresponding to a suspension of PVC in a plasticizing agent miscible with PVC, obtained in situ by heating at temperatures ranging from 60°C to 80°C; these plastisols may be those described in particular in the work “Polyurethane Sealants”, Robert M. Evans, ISBN 087762-998-6; and

[0159] - mixtures of these.

[0160] More preferably, the first composition and / or the second composition comprises, or consists of, at least one rheology agent (r1) and / or at least one rheology agent (r2), more preferably at least one rheology agent (r2).

[0161] Preferably, the rheology agent consists of at least one rheology agent (r2) (i.e., the rheology agent (r2) is the only rheology agent in the two-component composition, and more particularly in the first composition and / or the second composition). Preferably, the at least one rheology agent is present in the two-component composition in an amount of 0.5 to 15% by weight, more preferably 1 to 10% by weight, more preferably 1 to 5% by weight, relative to the total weight of the two-component composition; in particular in an amount of 0.5 to 1% by weight, or 1 to 2% by weight, or 2 to 3% by weight, or 3 to 4% by weight, or 4 to 5% by weight, or 5 to 7% by weight, or 7 to 10% by weight, or 10 to 15% by weight.

[0162] In other embodiments, the two-component composition according to the invention is devoid of rheology agent.

[0163] Rheology agent (r1)

[0164] By "amide waxes" is meant waxes comprising one or more compounds having at least one amide group. In particular, amide waxes can be obtained from fatty acid(s) (e.g. ricinoleic acid) and (di)amine(s).

[0165] The amide waxes are preferably micronized, that is to say they have an average particle size of less than 1 mm. Advantageously, the amide waxes have an average particle size of less than 500 pm, preferably less than 100 pm, more preferably less than 10 pm. The average particle size advantageously corresponds to the volume median diameter d50 and can be measured with a granulometer, in particular by laser diffraction, in particular on a MALVERN type device (for example according to standard NF ISO 13320).

[0166] Amide wax rheology agents are generally heat-activatable, i.e. a temperature above room temperature (23°C) may be necessary to activate it (in particular, activate its rheological properties) during the preparation of the composition according to the invention. The activation temperature depends on the rheology agent. Preferably, the activation temperature of the rheology agent (r1) is less than 80°C, more preferably less than 65°C, even more preferably less than 55°C.

[0167] Examples of commercial amide waxes are CRAYVALLAC® SLX or CRAYVALLAC® SLT marketed by Arkema, or THIXATROL® AS8053 or THIXATROL® MAX (EC No.: 432-430-3) which are available from ELEMENTIS.

[0168] Rheology agent (r2) Advantageously, the rheology agent (r2) is such that the bis-urea (a) is obtained by reaction of an n-alkylamine (a1) comprising from 1 to 22 carbon atoms, preferably n-butylamine, with a diisocyanate (a2) of formula (V)

[0169] NCO-R 6 -NCO (V) in which R 6 is chosen from one of the following divalent radicals, the formulas below of which show the 2 free valences:

[0170] - i) the derived divalent radical

[0171] - ii) the divalent radical 4,4'-methylene-bis(cyclohexyl):

[0172] - iii) the divalent radical derived from 2,4-toluene diisocyanate (or 2,4-TDI) OR 2,6-toluene diisocyanate (or 2,6-TDI), of respective formulae:

[0173] - iv) the divalent radical derived from 4,2'-diphenylmethylene diisocyanate (or 4,2'-MDI) or 4,4'-diphenylmethylene diisocyanate (or 4,4'-MDI), of respective formulae:

[0174] - v) the hexamethylene radical: -(CH2)e-,

[0175] - vi) the m-xylylene radical: - vii) the hexahydro-m-xylylene radical:

[0176] Preferably, the diisocyanate (a2) is of formula (V) in which R 6 is the divalent radical derived from 4,2'-MDI or 4,4'-MDI, preferably 4,4'-MDI.

[0177] According to a preferred embodiment, the bis-urea (a) is obtained by reaction of n-butylamine with a diisocyanate (a2) of formula (V) in which R 6 is the divalent radical derived from 4,2'-MDI or 4,4'-MDI, preferably 4,4'-MDI.

[0178] As indicated above, the plasticizer (b) is chosen from alkylphthalates, pentaerythritol tetravalerate, alkylsulfonic acid and phenol esters, diisononyl-1,2-cyclohexane dicarboxylate, 3,3'-

[0179] [methylenebis(oxymethylene)]bis[heptane], dioctyl carbonate and mixtures thereof.

[0180] The alkyl phthalates are preferably formed from the group consisting of diisodecyl phthalate (DIDP), di(2-propylheptyl) phthalate and mixtures thereof.

[0181] As regards pentaerythritol tetravalerate, we can cite the product marketed under the brand name Pevalen® by the company Perstorp.

[0182] As regards an ester of alkylsulfonic acid and phenol, we can cite the product Mesamoll®, marketed by the company Lanxess.

[0183] As regards diisononyl-1,2-cyclohexane dicarboxylate, we can cite the product marketed under the name Hexamoll Dinch® by the company BASF.

[0184] 3,3'-[methylenebis(oxymethylene)]bis[heptane] can be identified by its CAS number: 22174-70-5 and is also known under the trade name 2-ethylhexylal, available from LAMBIOTTE.

[0185] Dioctyl carbonate (EC No. 434-850-2) is available from BASF, for example.

[0186] Advantageously, the rheology agent (r2) is such that the plasticizer (b) is chosen from alkylphthalates, preferably the plasticizer (b) is chosen from diisodecyl phthalate, di(2-propylheptyl) phthalate and their mixtures, more preferably the plasticizer (b) is diisodecyl phthalate.

[0187] In a particularly preferred manner, the rheology agent (r2) consists of:

[0188] - from 1% to 40% by weight of a bis-urea (a) obtained by reaction of a primary aliphatic amine with a diisocyanate of molar mass less than 500 g / mol, relative to the total weight of the rheology agent (r2), and - from 60% to 99% by weight of a plasticizer (b) chosen from alkylphthalates, pentaerythritol tetravalerate, alkylsulfonic acid esters of phenol, diisononyl-1,2-cyclohexane dicarboxylate, 3,3'-[methylenebis(oxymethylene)]bis[heptane], dioctyl carbonate and mixtures thereof, relative to the total weight of the rheology agent (r2), said rheology agent (r2) being in the form of a suspension of solid particles of the bis-urea (a) in a continuous phase of plasticizer (b), and bis-urea (a) and the plasticizer (b) may be as described above (according to any of the embodiments described above).

[0189] Advantageously, the rheology agent (r2) comprises, and preferably consists of, from 5 to 30% by weight of the bis-urea (a) and from 70 to 95% by weight of the plasticizer (b), the percentages being relative to the total weight of said rheology agent (r2).

[0190] The bis-urea (a) and the plasticizer (b) are as described above.

[0191] The rheology agent (r2) can be prepared according to the method described below.

[0192] The reaction of the primary aliphatic amine with the diisocyanate is highly exothermic. To prevent the large amount of heat formed by the reaction from causing the decomposition of the bis-urea formed, the primary aliphatic amine and the diisocyanate are preferably each dissolved in the plasticizer (b), prior to their reaction, said plasticizer (b) thus serving to remove the heat formed by the reaction. The two solutions in the plasticizer (b) of the primary aliphatic amine and the diisocyanate are advantageously each introduced into a reactor by injectors, under a pressure of 4 to 20 MPa, preferably 8 to 12 MPa, the two solutions thus being brought into contact in the state of sprayed liquid. The quantities of reactants preferably correspond to a ratio (number of moles of primary aliphatic amine) / (number of moles of diisocyanate) of approximately 2.The bis-urea is produced by the reaction in the form of solid particles dispersed in a continuous phase of plasticizer b), the Brookfield viscosity of the corresponding suspension, measured at a temperature of 23°C, being generally between 1 and 50 Pa.s, preferably between 10 and 25 Pa.s.

[0193] Inorganic charge

[0194] Preferably, the two-component composition according to the invention comprises at least one inorganic filler. More particularly, the first composition and / or the second composition may comprise an inorganic filler. Even more particularly, only the first composition, or only the second composition, or each of the first and second compositions, comprises an inorganic filler. In the present text, by "inorganic filler", is meant a filler different from (and therefore additional to) the possible fillers comprising a hydroxide salt or thermally conductive fillers described above.

[0195] Advantageously, the second composition comprises at least one inorganic filler, more advantageously only the second composition comprises the at least one inorganic filler.

[0196] The average particle size of the inorganic filler can range from 10 nm to 400 pm, preferably from 20 nm to 100 pm, more preferably from 30 nm to 50 pm. The average particle size advantageously corresponds to the volume median diameter d50 and can be measured with a granulometer, in particular by laser diffraction, in particular on a MALVERN type device (for example according to standard NF ISO 13320).

[0197] Particularly preferably, the inorganic filler is chosen from clays, talc, kaolins, gypsum, carbonate fillers, zeolites, expandable graphite and mixtures thereof.

[0198] More preferably, the inorganic filler is chosen from carbonate fillers, zeolites, expandable graphite and their mixtures, more preferably from carbonate fillers.

[0199] Preferably, the carbonated fillers are formed by the group consisting of alkali or alkaline earth metal carbonates and their mixtures, more preferably the carbonated fillers are calcium carbonate or chalk, more preferably calcium carbonate, in particular precipitated calcium carbonate, more particularly precipitated calcium carbonate coated with fatty acids.

[0200] When calcium carbonate is coated with fatty acids, this makes the calcium carbonate particles completely or partially hydrophobic. In addition, the fatty acid coating acts as a hydrophobic coating that can prevent the calcium carbonate from absorbing the composition's constituents and rendering them ineffective. The hydrophobic coating of the calcium carbonate can represent from 0.1% to 3.5% by weight, based on the total weight of calcium carbonate.

[0201] Preferably, the fatty acids coating the calcium carbonate comprise or consist of more than 50% by weight of stearic acid relative to the total weight of fatty acids.

[0202] Examples of fatty acid-coated precipitated calcium carbonate include HAKUENKA® CCR-S10 (marketed by OMYA) or CALOFORT® SV14 (marketed by Specialty Minerals). The zeolites may be selected from synthetic zeolites of type A, X and / or Y, preferably type A, and preferably have a pore diameter of between 3 Å and 5 Å, more preferably 3 Å.

[0203] According to other preferred embodiments, the inorganic filler is precipitated calcium carbonate coated with fatty acids.

[0204] Advantageously, the amount of inorganic filler in the first composition, or in the second composition, or in each of the first and second compositions, preferably in the second composition, is from 1% to 25% by weight, preferably from 2% to 22% by weight, more preferably from 4% to 20% by weight, even more preferably from 10% to 18% by weight, relative to the total weight of said composition; for example from 1 to 5% by weight, or from 5 to 10% by weight, or from 10 to 12% by weight, or from 12 to 15% by weight, or from 15 to 18% by weight, or from 18 to 20% by weight, or from 20 to 25% by weight.

[0205] Membership Promoter

[0206] The first composition and / or the second composition may further comprise at least one adhesion promoter. Preferably, only one of the first and second compositions comprises at least one adhesion promoter. Preferably, the first composition comprises at least one adhesion promoter, more preferably only the first composition comprises the at least one adhesion promoter.

[0207] Advantageously, the adhesion promoter is chosen from amino-, mercapto-, isocyanurate- and epoxy-alkoxysilanes, preferably from isocyanurate- and aminoalkoxysilanes, more preferably from isocyanurate- and aminotrialkoxysilanes, even more preferably from isocyanurate- and aminotrimethoxysilanes.

[0208] An example of an epoxy-alkoxysilane is (3-glycidyloxypropyl)trimethoxysilane (also called GLYMO).

[0209] Advantageously, the isocyanurate- and aminotrimethoxysilanes are formed by the group consisting of 4-amino-3,3-dimethylbutyltrimethoxysilane (for example SILQUEST A-LINK 600 marketed by MOMENTIVE), (3-aminopropyl)trimethoxysilane (for example DYNASYLAN® AMMO marketed by EVONIK or Silquest* A-1110 marketed by Momentive), 1,3,5-tris[3-(trimethoxysilyl)propyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (CAS number: 26115-70-8) and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (for example DYNASYLAN® DAMO or DAMO-T marketed by EVONIK).

[0210] The adhesion promoter according to the invention may comprise a mixture of at least two adhesion promoters. In advantageous embodiments, the adhesion promoter comprises at least one aminotrimethoxysilane, preferably (3-aminopropyl)trimethoxysilane, and at least one isocyanurate-trimethoxysilane, preferably 1,3,5-tris[3-(trimethoxysilyl)propyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

[0211] The amount of adhesion promoter in the first composition, or in the second composition, or in each of the first and second compositions, preferably in the first composition, may be from 0.1 to 3% by weight, preferably from 0.2 to 2% by weight, more preferably from 0.5% to 1.6% by weight, relative to the total weight of said composition; in particular this amount may be from 0.1 to 0.5% by weight, or from 0.5 to 1% by weight, or from 1 to 1.2% by weight, or from 1.2 to 1.5% by weight, or from 1.5 to 1.7% by weight, or from 1.7 to 2% by weight, or from 2 to 2.5% by weight, or from 2.5 to 3% by weight.

[0212] Crosslinking catalyst

[0213] The second composition preferably further comprises a crosslinking catalyst. Particularly preferably, only the second composition comprises a crosslinking catalyst.

[0214] The crosslinking catalyst may be any catalyst known to those skilled in the art for silanol condensation. Examples of such catalysts include:

[0215] - organic titanium derivatives such as titanium acetyl acetonate (for example TYZOR® AA75 marketed by Dorf Ketal),

[0216] - aluminum such as aluminum chelate (for example K-KAT® 5218 marketed by KING INDUSTRIES),

[0217] - amines such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), diethyl ether-2,2'-morpholine (DMDEE) and / or 1,4-diazabicylo[2.2.2]octane (DABCO),

[0218] - catalysts based on zinc carboxylate and DBU (for example K-KAT® 670 marketed by KING INDUSTRIES),

[0219] - tin-based catalysts such as compounds derived from dioctyltin or dibutyltin; in particular dioctyltin oxide, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dicarboxylate, dibutyltin diacetylacetonate (DBTDAA), dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin oxide and / or the product resulting from the reaction of bis(acetyloxy)dioctylstannane with tetraethyl orthosilicate, preferably the product resulting from the reaction of bis(acetyloxy)dioctylstannane with tetraethyl orthosilicate. Examples include NEOSTANN® S-1 (marketed by KANEKA), or TIB KAT® 425 or TIB KAT® 423 (marketed by TIB CHEMICALS).Preferably, the crosslinking catalyst is a tin-based catalyst, more preferably chosen from compounds derived from dioctyltin and dibutyltin, more preferably the tin-based catalyst is derived from the reaction of bis(acetyloxy)dioctylstannane with tetraethyl orthosilicate (CAS number: 93925-43-0).

[0220] The content of crosslinking catalyst in the second composition may be from 0.01 to 1.5% by weight, preferably from 0.02 to 1.0% by weight, more preferably from 0.1 to 0.5% by weight, relative to the total weight of the second composition. In these embodiments, the content of crosslinking catalyst in the second composition is 0.01 to 0.05% by weight, or 0.05 to 0.1% by weight, or 0.1 to 0.2% by weight, or 0.2 to 0.3% by weight, or 0.3 to 0.4% by weight, or 0.4 to 0.5% by weight, or 0.5 to 0.7% by weight, or 0.7 to 1.0% by weight, or 1.0 to 1.5% by weight, relative to the total weight of the second composition

[0221] Flame retardant

[0222] The first composition and / or the second composition may further comprise a flame retardant. Preferably, only one of the first and second compositions comprises at least one flame retardant. Preferably, the second composition comprises at least one flame retardant, more preferably only the second composition comprises the at least one flame retardant. In the present text, the term "flame retardant" denotes a flame retardant other than the filler comprising a hydroxide salt.

[0223] Preferably, the flame retardant is chosen from triarylphosphates, trialkylphosphates and mixtures thereof, more preferably from tricresylphosphate, cresyldiphenylphosphate, tributylphosphate, trioctylphosphate, tris(2-ethylhexyl)phosphate, tris(chloroethyl)phosphate, tris(dichloropropyl)phosphate, tris(dibromopropyl)phosphate and mixtures thereof, even more preferably, the flame retardant is cresyldiphenylphosphate.

[0224] The amount of flame retardant (other than the filler comprising the hydroxide salt) in the first composition, or in the second composition, or in each of the first and second compositions, preferably in the second composition, may be from 0.5 to 20% by weight, preferably from 0.8% to 15% by weight, more preferably from 1% to 5% by weight, relative to the total weight of said composition; for example this amount may be from 0.5 to 0.8% by weight, or from 0.8 to 1% by weight, or from 1 to 1.2% by weight, or from 1.2 to 1.5% by weight, or from 1.5 to 1.7% by weight, or from 1.7 to 2% by weight, or from 2 to 2.5% by weight, or from 2.5 to 3% by weight, or from 3 to 5% by weight, or from 5 to 10% by weight, or from 10 to 15% by weight, or from 15 to 20% by weight.

[0225] Other additives

[0226] The two-component composition according to the invention may further comprise at least one additive. The additive may be present in the first composition and / or in the second composition. Preferably, the additive is chosen from the group consisting of plasticizers, solvents, UV stabilizers (or antioxidants) and mixtures thereof.

[0227] Advantageously, the two-component composition according to the invention comprises a mixture of several (at least two) additives chosen from plasticizers, solvents and UV stabilizers.

[0228] Water is not considered a solvent for the purposes of the invention.

[0229] The total content of additives may be from 0.1 to 20% by weight, preferably from 1 to 15% by weight, more preferably from 2 to 12% by weight, relative to the total weight of the two-component composition.

[0230] Advantageously, the first composition and / or the second composition of the two-component composition according to the invention comprises at least one additive chosen from plasticizers.

[0231] By "additive chosen from plasticizers" is meant a plasticizer different from the plasticizer (b) included in the rheology agent (r2), when the two-component composition comprises a rheology agent (r2). Preferably, the two-component composition, when it comprises a rheology agent (r2), further comprises at least one additive chosen from plasticizers (i.e., at least one other plasticizer).

[0232] In embodiments, only the first composition or only the second composition comprises at least one additive selected from plasticizers. In other embodiments, each of the first and second compositions comprises at least one additive selected from plasticizers, this additive selected from plasticizers being able to be identical or different in each of the two compositions.

[0233] The additive chosen from among the plasticizers can be any plasticizer usually used in the field of adhesive compositions.

[0234] Preferably, this plasticizer is chosen from:

[0235] - diisodecyl phthalate (for example PALATINOL® DIDP marketed by BASF),

[0236] - diisononyl phthalate (DINP) (for example PALATINOL® N marketed by BASF), - an ester of alkylsulfonic acid and phenol (for example MESAMOLL® marketed by LANXESS),

[0237] - diisononyl hexahydrophthalate (for example HEXAMOLL DINCH® marketed by BASF),

[0238] - pentaerythritol tetravalerate (for example PEVALEN™ marketed by PERSTORP),

[0239] - alkyl and fatty acid esters, in particular fatty acid methyl esters, for example those prepared from castor oil (for example Esterol A Oleris® marketed by Arkema).

[0240] More preferably, this plasticizer is diisononyl hexahydrophthalate and / or fatty acid methyl esters.

[0241] The amount of additive chosen from plasticizers in the first composition, or in the second composition, or in each of the first and second compositions, may advantageously be from 1 to 30% by weight, preferably from 2% to 20% by weight, more preferably from 3 to 18% by weight, relative to the total weight of said composition (for example from 1 to 3% by weight, or from 3 to 5% by weight, or from 5 to 7% by weight, or from 7 to 10% by weight, or from 10 to 15% by weight, or from 15 to 20% by weight, or from 20 to 25% by weight).

[0242] In embodiments, the amount of additive selected from plasticizers in the two-component composition may be from 2 to 15% by weight, preferably from 3 to 12% by weight, for example from 4 to 10% by weight, relative to the total weight of the two-component composition.

[0243] The two-component composition according to the invention may comprise from 0 to 5% by weight of a solvent relative to the total weight of said two-component composition, preferably a solvent which is volatile at room temperature (temperature of the order of 23°C). The volatile solvent may for example be chosen from alcohols which are volatile at room temperature, such as ethanol or isopropanol. Preferably, the two-component composition comprises from 0 to 1% by weight of a solvent relative to the total weight of said two-component composition, more preferably from 0 to 0.5% by weight.

[0244] Advantageously, the two-component 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 said two-component composition (for example from 0.01 to 1% by weight), preferably up to 0.5% by weight. The UV stabilizers are typically introduced to protect the composition from degradation resulting from a reaction with oxygen which is likely to form by the action of heat or light. These compounds may include antioxidants capable of trapping free radicals.Advantageously, the UV stabilizer(s) (or antioxidants) are chosen from benzotriazoles, benzophenones, so-called hindered phenols such as octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (CAS No.: 2082-79-3), pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (CAS No.: 6683-19-8) and ethylenebis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] (CAS No.: 36443-68-2), so-called hindered amines such as bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate (CAS No. 41556-26-7), methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate (CAS No. 82919-37-7), octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 4,4'-bis(a,a-dimethylbenzyl)diphenylamine, and mixtures thereof.Examples include the products IRGANOX 1076, TINUVIN® 292, TINUVIN® 765 or TINUVIN® 770 DF marketed by BASF, RIASORB UV-123 marketed by RIANLON and OKABEST CLX 50 marketed by OKA.

[0245] Preferably, the UV stabilizer(s) (or antioxidant(s)) are chosen from so-called hindered phenols and amines and mixtures thereof.

[0246] More preferably, the UV stabilizers (or antioxidants) are a mixture of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and 4,4'-bis(a,a-dimethylbenzyl)diphenylamine.

[0247] Advantageously, the two-component composition according to the invention does not comprise a moisture absorber, in particular chosen from vinyltrimethoxysilane, vinyltriethoxysilane, alkoxyarylsilanes and p-toluenesulfonyl isocyanate.

[0248] The two-component composition according to the invention may comprise free water (in particular in the second composition, more particularly only in the second composition). By "free water" is meant water added to the composition, as opposed to moisture inherently present in the ingredients of the composition. Preferably, the free water content in the two-component composition is less than or equal to 0.03% by weight, preferably less than or equal to 0.01% by weight, more preferably less than or equal to 0.005% by weight, relative to the total weight of the two-component composition. More preferably, the two-component composition is free of free water.

[0249] Two-component composition

[0250] Advantageously, the volume ratio of the first composition relative to the second composition is between 0.25 and 4, preferably between 0.5 and 2.5, more preferably between 0.8 and 2.2. It may for example be between 0.8 and 1.2 and be more particularly equal to 1.0 or be between 1.5 and 2.2, and be more particularly equal to 2.0.

[0251] Preferably, the two-component composition according to the invention comprises:

[0252] - at least one silylated polymer in the first composition, preferably in an amount of 3% to 40% relative to the total weight of the first composition;

[0253] - at least one filler comprising a hydroxide salt in one of the first and second compositions, preferably in the first composition, preferably in an amount of 1% to 90% by weight relative to the total weight of the composition in which it is present;

[0254] - at least one acid in the other of the first and second compositions, preferably in the second composition, preferably in an amount of 0.1% to 10% relative to the total weight of the composition in which it is present;

[0255] - at least one additional thermally conductive filler, in the first composition and / or in the second composition, preferably in an amount of 40% to 90% by weight relative to the total weight of the composition in which it is present;

[0256] - optionally at least one rheology agent, preferably a rheology agent (r1) and / or a rheology agent (r2), in the first composition and / or in the second composition, preferably in the first composition, preferably in an amount of 0.5% to 15% by weight relative to the total weight of the two-component composition;

[0257] - at least one inorganic filler in the first composition and / or in the second composition, preferably in the second composition, preferably in an amount of 1% to 25% by weight relative to the total weight of the composition in which it is present;

[0258] - at least one adhesion promoter in the first composition and / or in the second composition, preferably in the first composition, preferably in an amount of 0.1 to 3% by weight relative to the total weight of the composition in which it is present;

[0259] - at least one crosslinking catalyst in the second composition, preferably in an amount of 0.01 to 1.5% by weight relative to the total weight of the second composition;

[0260] - at least one flame retardant in the first composition and / or in the second composition, preferably in the second composition, preferably in an amount of 0.5 to 20% by weight relative to the total weight of the composition in which it is present; - one or more additives chosen from plasticizers, solvents, UV stabilizers and their mixtures, preferably in an amount of 0.1 to 20% by weight relative to the total weight of the two-component composition, these additives more preferably comprising:

[0261] ■ at least one additive chosen from plasticizers in the first composition and / or in the second composition, preferably in an amount of 1 to 30% by weight relative to the total weight of the composition in which it is present; and

[0262] ■ at least one UV stabilizer in the first composition and / or in the second composition, preferably in the first composition, preferably in an amount of 0.01 to 1% relative to the total weight of the composition in which it is present; the volume ratio of the first composition relative to the second composition being between 0.25 and 4.

[0263] More preferably, the two-component composition consists of, or consists essentially of, the ingredients mentioned above. By "the composition consists essentially of", it is meant that the two-component composition according to the invention comprises less than 5% by weight of ingredients other than the aforementioned ingredients, relative to the total weight of said two-component composition, preferably less than 2% by weight, even more preferably less than 1% by weight.

[0264] The above-mentioned ingredients may be more particularly as described in the preceding sections, in particular with regard to their nature, quantity and presence in the first or second compositions, in all possible combinations.

[0265] Advantageously, the two-component composition comprises:

[0266] - a first composition comprising, consisting essentially of, or consisting of, relative to the total weight of the first composition:

[0267] ■ from 3% to 40% by weight of silylated polymer;

[0268] ■ from 40 to 85% by weight of at least one filler comprising a hydroxide salt;

[0269] ■ from 0 to 40% by weight of at least one thermally conductive filler;

[0270] ■ from 0 to 15% by weight of at least one rheology agent, preferably a rheology agent (r1) and / or a rheology agent (r2);

[0271] ■ from 0.1 to 3% by weight of at least one adhesion promoter;

[0272] ■ from 0 to 10% by weight of at least one additive chosen from plasticizers; and

[0273] ■ from 0.01 to 1% by weight of at least one UV stabilizer; and / or, preferably and,

[0274] - a second composition comprising, consisting essentially of, or consisting of, relative to the total weight of the second composition:

[0275] ■ from 0.1 to 10% by weight of at least one acid;

[0276] ■ from 40% to 90% by weight of at least one thermally conductive filler;

[0277] ■ from 1% to 25% by weight of at least one inorganic filler;

[0278] ■ from 0.5 to 20% by weight of at least one flame retardant;

[0279] ■ from 0.01 to 1.5% by weight of at least one crosslinking catalyst; and

[0280] ■ from 1 to 30% by weight of at least one additive chosen from plasticizers; the volume ratio of the first composition relative to the second composition preferably being between 0.25 and 4.

[0281] The above-mentioned ingredients may be more particularly as described in the preceding sections, in particular with regard to their nature and quantity, in all possible combinations.

[0282] Advantageously, the viscosity at 21°C of the two-component composition according to the invention is less than or equal to 300 Pa.s (300,000 cP), preferably between 100 Pa.s and 280 Pa.s (between 100,000 cP and 280,000 cP). The viscosity at 21°C of the two-component composition according to the invention is preferably determined immediately after it has been obtained at 20 rpm (revolutions per minute) and using a Brookfield RVT viscometer and a size 7 needle.

[0283] The creep of the two-component composition according to the invention is advantageously less than 2.54 cm (1 inch) at 23°C. The creep can be determined according to ASTM D2202.

[0284] Preparation of the two-component composition

[0285] Each of the first and second compositions of the two-component composition according to the invention is prepared separately, by simple mixing of its ingredients, in one or more stages, preferably in several stages, preferably under vacuum.

[0286] By "vacuum" is meant a pressure lower than atmospheric pressure, advantageously between 10 kPa and 90 kPa, preferably between 50 kPa and 85 kPa, more preferably between 60 kPa and 80 kPa.

[0287] Advantageously, the two-component composition according to the invention is prepared without adding free water, that is to say other than that inherently included in the ingredients of the composition.

[0288] According to preferred embodiments, the first composition is prepared according to the following method: - 1) the silylated polymer is mixed, in a suitable container, with the possible adhesion promoter, the possible flame retardant and with the possible additives such as solvents and UV stabilizers (or antioxidants), optionally the possible additives chosen from plasticizers, preferably at a temperature between 18°C ​​and 28°C and under vacuum, then

[0289] - 2) the possible thermally conductive filler(s), the possible filler(s) comprising a hydroxide salt and the possible inorganic filler(s) are dispersed in the preceding mixture at the same pressure, until a homogeneous mixture is obtained, then

[0290] - 3) the possible rheology agent, the possible acid, and optionally the possible additives chosen from among the plasticizers, are added at the same pressure and the medium is homogenized.

[0291] According to preferred embodiments, the second composition is prepared according to the following method:

[0292] - 1) the possible adhesion promoter and / or the possible flame retardant and the possible additives such as plasticizer, solvent and UV stabilizer (or antioxidant) are mixed, preferably at a temperature between 18°C ​​and 28°C and under vacuum, then

[0293] - 2) the possible inorganic filler(s), the possible thermally conductive filler(s) and the possible filler(s) comprising a hydroxide salt are dispersed in the preceding mixture at the same pressure, until a homogeneous mixture is obtained, then

[0294] - 3) the possible rheology agent is added at the same pressure and the medium is homogenized, then

[0295] - 4) the possible crosslinking catalyst and the possible acid are added at the same pressure and the medium is homogenized.

[0296] Preferably, the temperature during the preparation of the second composition is less than or equal to 50°C, more preferably less than or equal to 45°C, even more preferably less than or equal to 40°C.

[0297] An example of preparation of the first and second compositions and of the two-component composition according to the invention is described in Example 1 below.

[0298] The first and second compositions may be packaged, for example, in a dual cartridge. The two-component composition is then advantageously dispensed using a dual cartridge gun. A homogeneous mixture of the two compositions is obtained by attaching, for example, a static mixer to the dual cartridge. Use of the two-component composition

[0299] The present invention also relates to the use of the two-component composition according to the invention (i.e., as described above) as an adhesive and / or sealant, preferably as an adhesive.

[0300] In particular, the present invention also relates to the use of the two-component composition according to the invention as an adhesive in the field of building construction, in the field of manufacturing means of transport, preferably in the automotive, railway or aerospace industry, or in the field of shipbuilding, more particularly for assemblies intended for the manufacture of batteries, in particular rechargeable batteries for electric cars or hybrid cars. Thus, the invention relates in particular to the use of the two-component composition according to the invention as an adhesive and / or sealant in a battery, preferably a rechargeable battery.

[0301] The present invention also relates to the use of the two-component composition according to the invention for improving the lifespan of a battery, preferably a rechargeable battery.

[0302] The invention also relates to a method of manufacturing a battery, preferably rechargeable, comprising the assembly of said battery using a two-component composition according to the invention as adhesive and / or sealant.

[0303] Furthermore, the invention also relates to the use of a filler comprising a hydroxide salt in combination with an acid, for crosslinking without adding free water of a two-component composition, the two-component composition comprising a first composition comprising a silylated polymer, and a second composition, one of the first and second compositions comprising the filler comprising a hydroxide salt, and the other of the first and second compositions comprising the acid.

[0304] The two-component composition, the first composition, the second composition, the silylated polymer, the filler comprising a hydroxide salt and the acid may be as described above.

[0305] The present invention also relates to a method of assembling two substrates by gluing, comprising:

[0306] - coating on at least one of the two substrates to be assembled with the two-component composition according to the invention, then

[0307] - the effective contact of the two substrates.

[0308] The substrates concerned are very varied and are, for example, inorganic substrates such as concrete, metals or alloys (such as aluminum alloys, steel, non-ferrous metals and galvanized metals); or organic substrates such as wood, plastics such as PVC, polycarbonate, PMMA, polyethylene, polypropylene, polyesters, epoxy resins; or metal substrates and composites coated with paint (as in the automotive field for example). Preferably, the substrates are metals and / or plastics.

[0309] The invention also relates to a method for crosslinking a two-component composition as described above, comprising contacting, and preferably mixing, the first composition with the second composition.

[0310] The present invention also relates to an article, in particular a battery, comprising the two-component composition according to the invention. The invention also relates to an article comprising a composition as obtained by bringing into contact, preferably by mixing, the first composition with the second composition of a two-component composition according to the invention. Preferably, the article according to the invention is a battery, in particular a rechargeable battery, more preferably for an electric or hybrid car.

[0311] All the embodiments described above can be combined with each other. In particular, the various aforementioned ingredients of the two-component composition according to the invention, and in particular the preferred embodiments, and in all their amounts, can be combined with each other.

[0312] The following examples illustrate the invention without limiting it.

[0313] Ingredients used

[0314] The following ingredients were used:

[0315] - Kaneka Silyl™ MA490 marketed by KANEKA: poly(propylene oxide) / polyacrylate with trimethoxysilane ends, having a viscosity of 180 Pa.s;

[0316] - AI2O3: spherical alumina with a median diameter d50 of 12.5 pm (thermally conductive filler)

[0317] - Rheology agent (r2), prepared as indicated below;

[0318] - Hexamoll® DINCH marketed by BASF: diisononyl ester of 1,2-cyclohexanedicarboxylic acid (plasticizer);

[0319] - APYRAL® 20HC marketed by Nabaltec: aluminum hydroxide with a hydrophobic surface treatment, having a median diameter d50 of 30 pm (thermally conductive filler); - Dynasylan® VPS 7163 marketed by Evonik: 1,3,5-tris[3-(trimethoxysilyl)propyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (CAS number: 26115-70-8) (adhesion promoter);

[0320] - Silquest* A-1110 marketed by Momentive: (3-aminopropyl)trimethoxysilane (adhesion promoter);

[0321] - Okabest® CLX 50 marketed by OKA: mixture of 78 mol% of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (CAS number 2082-79-3) and 22 mol% of 4,4'-bis(a,a-dimethylbenzyl)diphenylamine (CAS number: 10081-67-1) (UV stabilizer);

[0322] - Esterai A Oleris® marketed by Arkema: methyl esters of fatty acids prepared from castor oil (plasticizer);

[0323] - Disflamoll® DPK marketed by LANXESS: cresyldiphenylphosphate (CDP) (flame retardant);

[0324] - Calofort® SV14 marketed by Specialty Minerals: precipitated calcium carbonate coated with calcium stearate, with an average particle size of 70 nm (inorganic filler);

[0325] - Neostann™ S-1 marketed by KANEKA: product resulting from the reaction of bis(acetyloxy)dioctylstannane with tetraethyl orthosilicate (CAS number: 93925-43-0) (crosslinking catalyst);

[0326] - 100% phosphoric acid.

[0327] Preparation of the rheology sample (r2)

[0328] The following ingredients were used to prepare the rheology agent (r2):

[0329] - n-butylamine (primary aliphatic amine for the preparation of bis-urea (a));

[0330] - 4,4'-diphenylmethane diisocyanate (4,4'-MDI) (diisocyanate for the preparation of bis-urea (a));

[0331] - diisodecyl phthalate (DIDP) (plasticizer (b)).

[0332] The rheology agent (r2) was obtained as follows. Two solutions were prepared:

[0333] - a solution A of n-butylamine in DIDP, consisting of 17.17% by weight of n-butylamine and 82.83% by weight of DIDP, relative to the total weight of solution A, and - a solution B of 4,4'-MDI in DIDP, consisting of 29.46% by weight of 4,4'-MDI in 70.54% by weight of DIDP, relative to the total weight of solution B.

[0334] The 2 solutions A and B were heated to 100°C, then introduced, each under a pressure of 100 bar, into a reactor, in which they were continuously sprayed onto each other in a mass ratio A / B of 50.1 / 49.9, corresponding to a molar ratio n-butylamine / 4,4'-MDI equal to 2. The reaction was immediate and the temperature of the reactor reached 140°C at the end of manufacture.

[0335] At the reactor outlet, a stable dispersion of 23.3% by weight (relative to the total weight of the dispersion) in the DIDP of a bis-urea of ​​formula:

[0336] The Brookfield viscosity of the suspension measured at 23°C is 15 Pa.s.

[0337] Preparation of the compositions

[0338] Each of the first compositions (called “composition A” below) and the second compositions (called “composition B” below) forming the two-component compositions tested were prepared by mixing the ingredients in the quantities indicated in the table below (in mass percentage relative to the total weight of the respective compositions A or B in which these ingredients are added).

[0339] Table 1

[0340]

[0341] Two-component composition No. 1 is a comparative composition, two-component compositions No. 2 and 3 are compositions according to the invention.

[0342] The ingredients of each of compositions A and B were mixed in a reactor maintained under stirring in several stages as described below. The reactor is at room temperature (approximately 23°C) before addition of the ingredients, and the temperature may increase as the ingredients are mixed. The temperature was controlled not to exceed 40°C during the preparation of compositions B. At each stage of addition of the ingredients, these were mixed under vacuum (between 60 kPa and 80 kPa) and at a stirring speed sufficient to homogenize the mixture.

[0343] Regarding the preparation of compositions A, the silylated polymer, the UV stabilizer and the adhesion promoters are added in a first step, then the alumina (when present) and the aluminum hydroxide are added slowly in a second step, then the rheology agent (r2) or the plasticizer DINCH is added in a third step.

[0344] Regarding the preparation of compositions B, the flame retardant CDP and Esterol A Oleris® are added in a first step, then the alumina, aluminum hydroxide (when present) and the filler Calofort® SV14 are added slowly in a second step, then the crosslinking catalyst Neostann S-1 and phosphoric acid (when present) are added in a third step.

[0345] The final compositions No. 1', 2' and 3' were prepared from the two-component compositions No. 1, 2 and 3, respectively, according to the following process: compositions A and B of the two-component composition were introduced into a bi-cartridge (protected from air and humidity), then mixed using a dynamic mixer attached to the tip of the bi-cartridge, at room temperature (23°C) in a volume ratio A:B equal to 2:1. measured

[0346] The following properties were measured for compositions 1', 2' and 3':

[0347] - Elongation at break and tensile strength: measured in accordance with ISO 37 (2005), at a constant speed of 500 mm / min.

[0348] Specifically, the following conditions were applied: a standard dumbbell-shaped test piece, type 2, as illustrated in the international standard ISO 37 (2005) was used. The narrow part of the dumbbell used has a length of 20 mm, a width of 4 mm and a thickness of 3 to 4 mm. To prepare the dumbbell, the composition to be tested was applied in a Teflon mold, and the composition was allowed to crosslink for 14 days under standard conditions (23°C and 50% relative humidity).

[0349] The principle of the measurement consists of stretching a standard test piece in a tensile machine, whose movable jaw moves at a constant speed equal to 500 mm / minute, and recording:

[0350] ■ the elongation at break (expressed in %), which is the elongation of the specimen corresponding to the stretching observed at the time of break, and

[0351] ■ the tensile strength (in MPa), which is the tensile stress at which the specimen ruptures.

[0352] The measurement was repeated for 5 specimens, and the corresponding average of the results obtained was calculated.

[0353] - Crosslinking: The crosslinking depth was determined using the following method. A Teflon tray with increasing depth from 1 mm to 10 mm is filled with the composition to be tested. The length to depth ratio of 20 / 1 is constant along the entire length of the tray. For example, at 2 cm in length, the depth of the tray is 1 mm, at 10 cm in length, the depth of the tray is 5 mm, and at 20 cm in length, the depth of the tray is 10 mm. The tray has the following dimensions:

[0354] ■ block dimensions: 25 x 5 x 2 cm,

[0355] ■ recess dimensions: 20 x 2 x 1 mm to 10 mm.

[0356] After filling with the composition to be tested, the gutter is left in controlled humidity and temperature conditions (23°C and 50% relative humidity) for 24 hours. After these 24 hours, the strip is pulled on the thinnest part (i.e. 1 mm) until the non-crosslinked part is reached, i.e. a soft, non-cohesive part, which tends to remain in the gutter. The corresponding fully crosslinked thickness is noted.

[0357] - Shear strength measured according to the following method:

[0358] Two rectangular aluminum plates measuring 100 mm x 25 mm x 2 mm are used. After cleaning the two plates with acetone, a rectangular bonding area measuring 12.5 mm x 25 mm is defined, using adhesive tape, at the end of each plate.

[0359] On the gluing area of ​​a 1 èresubstrate plate thus materialized, the composition to be tested is applied, in a quantity corresponding to a thickness of 2 mm. Then the bonding zone of the 2 is superimposed on the area thus coated ème substrate plate, so as to obtain an assembly in which the free ends of the 2 substrate plates are aligned on either side of the two areas joined by the composition. The assembly specimen obtained is held by clips for 14 days in a room with a controlled atmosphere at 23°C and 50% relative humidity, for crosslinking of the composition.

[0360] The two free ends of the specimen are pulled by means of a tensile machine at a constant speed equal to 50 mm / minute, until the assembly breaks, for which the applied stress is recorded.

[0361] The measurement was repeated for 3 assembly specimens, and the average of the shear stresses at failure (referred to as shear strength) obtained was calculated.

[0362] Results

[0363] The results obtained are presented in the table below.

[0364] Table 2 It is observed that compositions No. 2' and 3' according to the invention exhibit crosslinking greater than that of the comparative composition 1' not comprising phosphoric acid. During the test measuring the depth of crosslinking, the samples of composition No. 2' and 3' crosslinked to the core (or even completely with regard to composition No. 2' comprising a greater quantity of phosphoric acid), whereas for the sample of composition No. 1' only an external part crosslinked. Indeed, for composition No. 1, only the part in contact with the air (and therefore with the humidity of the air) was able to crosslink. These results demonstrate that the presence of phosphoric acid allowed the creation of humidity, allowing good crosslinking of the composition (including in depth) even in the absence of the addition of water in the two components of the initial two-component composition.

[0365] Furthermore, compositions No. 2' and 3' exhibit higher shear strength than comparative composition No. 1'. In this shear strength test, the composition was placed between two metal plates and therefore had no contact with the air and the moisture present in it. Under these conditions, composition No. 1' did not crosslink and remained liquid. In contrast, compositions No. 2' and 3' underwent complete crosslinking (evidenced by their high shear strength). These results confirm that water formed within these compositions, leading to their crosslinking.

[0366] Finally, it is observed that compositions No. 2' and 3' according to the invention have good mechanical properties.

Claims

Claims 1. Two-component composition comprising at least: a first composition comprising a silylated polymer comprising at least one alkoxysilane group; and a second composition; in which: one of the compositions among the first and second compositions comprises at least one filler comprising a hydroxide salt, and the other of the compositions among the first and second compositions comprises at least one acid being a Brônsted acid.

2. Two-component composition according to claim 1, in which the at least one filler comprising a hydroxide salt is a thermally conductive filler.

3. A two-component composition according to claim 1 or 2, wherein the at least one filler comprising a hydroxide salt is selected from the group consisting of aluminum hydroxide, calcium hydroxide, magnesium hydroxide, cadmium hydroxide, lead(II) hydroxide, zinc hydroxide, strontium hydroxide, barium hydroxide, beryllium hydroxide, silver(I) hydroxide, iron hydroxides, nickel(II) hydroxide and mixtures thereof, preferably from the group consisting of aluminum hydroxide, calcium hydroxide, magnesium hydroxide and mixtures thereof, more preferably the filler comprising a hydroxide salt is aluminum hydroxide.

4. Two-component composition according to one of claims 1 to 3, in which the at least one acid is a Brônsted acid chosen from the group consisting of phosphoric acid, pyrophosphoric acid, polyphosphoric acids, organic phosphates, phosphonic acids, phosphonates, sulfonic acids, carboxylic acids and combinations thereof. ci, more preferably chosen from the group consisting of phosphoric acid, pyrophosphoric acid, polyphosphoric acids, salicylic acid and mixtures thereof.

5. Two-component composition according to one of claims 1 to 4, in which the Brônsted acid has a pka at 25°C less than or equal to 6.

6. Two-component composition according to one of claims 1 to 5, in which the first composition and / or the second composition further comprises at least one additional thermally conductive filler, different from the filler comprising a hydroxide salt.

7. Two-component composition according to claim 6, wherein the at least one additional thermally conductive filler is selected from the group consisting of aluminosilicates, alumina, aluminum nitride, boron nitride, zinc oxide, magnesium oxide and mixtures thereof, preferably from the group consisting of aluminosilicates, alumina and mixtures thereof.

8. Two-component composition according to one of claims 1 to 7, in which the first composition and / or the second composition further comprises at least one inorganic filler, preferably chosen from the group of clays, talc, kaolins, gypsum, carbonate fillers, such as precipitated calcium carbonate, zeolites, expandable graphite and mixtures thereof.

9. Two-component composition according to one of claims 1 to 8, in which the silylated polymer comprises at least one, preferably at least two, alkoxysilane groups of formula (I): -If(R 4 ) P (GOLD 5 )3.p (I) in which: R 4 represents a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, and when p is equal to 2, the radicals R 4 are the same or different, R 5represents a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, and when p is equal to 0 or 1, the radicals R 5 are identical or different, two OR groups 5 which can be engaged in the same cycle, and p is an integer equal to 0, 1 or 2, preferably equal to 0 or 1.

10. Two-component composition according to claim 9, in which the silylated polymer comprises a polymer of formula (II), (III) or (IV): in which: R 4 , R 5 and p have the same meaning as in formula (I) described above, P represents a saturated or unsaturated polymeric radical, with a linear or branched open chain, or comprising one or more optionally aromatic cycles, optionally comprising one or more heteroatoms, such as oxygen, nitrogen, sulfur and / or silicon, preferably oxygen and / or nitrogen, R 1represents a divalent hydrocarbon radical comprising from 5 to 15 carbon atoms, saturated or unsaturated, with a linear or branched open chain, or comprising one or more optionally aromatic cycles, R 3 represents a linear or branched divalent alkylene radical comprising from 1 to 6 carbon atoms, preferably from 1 to 3 carbon atoms, - X represents a divalent radical chosen from -NH-, -NR 7 - or - S-, R 7 represents a linear or branched alkyl radical comprising from 1 to 20 carbon atoms and which may also comprise one or more heteroatoms, f is an integer ranging from 1 to 6, preferably from 2 to 5, more preferably from 2 to 4, even more preferably from 2 to 3.

11. Two-component composition according to one of claims 1 to 10, in which the first composition and / or the second composition further comprises at least one rheology agent, the at least one rheology agent preferably comprising: at least one rheology agent (r1) chosen from amide waxes; and / or a rheology agent (r2) comprising, relative to the total weight of the rheology agent (r2): ■ from 1% to 40% by weight of at least one bis-urea (a) obtained by reaction of a primary aliphatic amine with a diisocyanate of molar mass less than 500 g / mol, and ■ from 60% to 99% by weight of at least one plasticizer (b) selected from the group consisting of alkylphthalates, pentaerythritol tetravalerate, alkylsulfonic acid esters of phenol, diisononyl-1,2-cyclohexane dicarboxylate, 3,3-[methylenebis(oxymethylene)]bis[heptane], dioctyl carbonate and mixtures thereof, said rheology agent (r2) being in the form of a suspension of solid particles of the at least one bis-urea (a) in a continuous phase of plasticizer (b).

12. Two-component composition according to claim 11, in which the rheology agent (r2) is such that the at least one bis-urea (a) is obtained by reaction of an n-alkylamine (a1) comprising from 1 to 22 carbon atoms, preferably n-butylamine, with a diisocyanate (a2) of formula (V): NCO-R 6 -NCO (V) in which R 6 is chosen from one of the following divalent radicals: the divalent radical derived from isophorone: the divalent radical 4,4'-methylene-bis(cyclohexyl): the divalent radical derived from 2,4-toluene diisocyanate or 2,6-toluene diisocyanate of respective formulas: the divalent radical derived from 4,2'-diphenylmethylene diisocyanate or 4,4'-diphenylmethylene diisocyanate, of respective formulas: the hexamethylene radical: -(CH2)e-, the m-xylylene radical: , and the hexahydro-m-xylylene radical:

13. Two-component composition according to one of claims 1 to 12, in which the volume ratio of the first composition relative to the second composition is from 0.25 to 4, preferably from 0.5 to 2.5, more preferably from 0.8 to 2.

2.

14. Two-component composition according to one of claims 1 to 13, comprising a free water content of less than or equal to 0.03% by weight, preferably less than or equal to 0.01% by weight, more preferably less than or equal to 0.005% by weight.

15. Use of the two-component composition according to one of claims 1 to 14 as an adhesive and / or sealant in a battery, preferably a rechargeable battery.

16. Method for crosslinking a two-component composition according to one of claims 1 to 14, comprising bringing the first composition into contact with the second composition.

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