Thermally conductive composition based on (METH)acrylate compounds

Abstract

The present invention relates to a crosslinkable two-component composition comprising: a component A, comprising: an oxidant; at least one (meth)acrylate monomer; a component B comprising: a reducing agent; said composition comprising at least one thermally conductive filler in component A and / or B; the composition having, after crosslinking, a density at 23°C of 1.6 to 2.2; the composition having, after crosslinking, a ratio of density at 23° C / thermal conductivity of 0.80 to 1.30; and the composition being free of compounds comprising a peroxide group.

Description

[0001] Thermally conductive composition based on (meth)acrylate compounds

[0002] FIELD OF INVENTION

[0003] The present invention relates to a thermally conductive composition based on a (meth)acrylate compound.

[0004] The invention also relates to the use of said composition for bonding, in particular in electric vehicle batteries.

[0005] TECHNOLOGICAL BACKGROUND

[0006] As technology evolves towards sustainable energy and transportation, electric mobility is becoming increasingly important.

[0007] Temperature management plays a key role in electric vehicle batteries. Battery cells can only deliver maximum performance within a specific temperature range and must not overheat. Furthermore, heating modern lithium-ion batteries can trigger a thermal reaction, which can escalate and cause a fire or even an explosion within the battery. The need to rapidly dissipate the heat generated during battery cell operation is increasingly crucial for batteries that are expected to achieve ever-greater performance. While silylated polymer-based thermally conductive compositions are available on the market, these compositions function more like conductive sealants and lack the mechanical properties suitable for structural or semi-structural bonding. Specifically, they are not designed to withstand stresses exceeding 7 MPa at 23°C (70 kg / cm²).2 They also cannot be reliably subjected to a high percentage of their maximum resistance for a long period of time under hostile conditions (low temperatures, heat, chemical agents, etc.).

[0008] Acrylic compositions are known reactive systems that crosslink by radical polymerization. Radical polymerization is typically initiated by a redox system which, through a redox reaction, leads to the production of radicals. The majority of acrylic systems are two-component systems. The first component traditionally contains the reducing agent and reactive monomers, and the second component contains the oxidizing agent. Once the two components are mixed, the reducing agent induces the cleavage of the O-O bond of the organic peroxide, for example, and initiates polymerization. Most current acrylic systems use peroxide / amine pairs to initiate the redox reaction and are most often offered as 10:1 two-component formulations without methacrylate in the hardener portion to ensure good long-term stability.

[0009] Currently, there are few thermally conductive acrylic compositions suitable for the electric vehicle market. Existing solutions generally result in rather brittle and rigid bonds / seals, which fail to withstand the vibrations experienced by electric vehicles in motion, and / or poor adhesion to specific substrates such as aluminum. Furthermore, the thermally conductive filler content is often high to achieve good thermal conductivity, which can lead to stability issues during storage (filler settling). Storage instability also negatively impacts production rates. The electric vehicle market is also increasingly seeking solutions to reduce battery weight.

[0010] Therefore, there is a need to find a composition that addresses at least partially one or more of the aforementioned disadvantages.

[0011] In particular, there is a need for compositions exhibiting good thermal conductivity (after crosslinking), good storage stability, and good adhesion to aluminum-type substrates.

[0012] More specifically, there is a need for compositions that offer a good compromise between sufficient thermal conductivity (after crosslinking), low density, storage stability, good reactivity, and mechanical performance (especially a good compromise between hardness and flexibility).

[0013] DESCRIPTION OF THE INVENTION

[0014] A. Composition

[0015] The present invention relates to a two-component crosslinkable composition comprising:

[0016] - a component A comprising:

[0017] • an oxidant;

[0018] • at least one (meth)acrylate monomer;

[0019] - a component B comprising:

[0020] • a reducer;

[0021] said composition comprising at least one thermally conductive filler in component A and / or B;

[0022] said composition having, after crosslinking, a density at 23°C ranging from 1.6 to 2.2; said composition having, after crosslinking, a density at 23°C / thermal conductivity ratio ranging from 0.80 to 1.30;

[0023] said composition being devoid of compounds comprising a peroxide group.

[0024] Preferably, crosslinking is carried out at 23°C and even more preferably at 50% relative humidity, for 24 hours.

[0025] Compounds containing a peroxide group -OO- include, in particular, R'-OOR type compounds i , R k -OOH (hydroperoxides), R lC(=O)-OOH, and peroxides including the peroxide anion [OO] 2- .

[0026] The composition according to the invention advantageously offers at least one of the following advantages:

[0027] good adhesion to aluminium-type substrates;

[0028] good stability to sedimentation over time;

[0029] good responsiveness, even after the composition has aged over time;

[0030] good thermal conductivity after crosslinking, while having a low density in order to meet the weight reduction requirements of electric batteries in the automotive field in particular;

[0031] a good compromise between hardness and flexibility with an elongation at break preferably greater than or equal to 6% to allow resistance to vibrations when vehicles with an electric battery are in motion;

[0032] a significantly reduced or even absent odor.

[0033] In the context of the invention, "alkyl" means a linear or branched hydrocarbon radical preferably comprising from 1 to 20 carbon atoms. Examples include methyl, ethyl, and propyl.

[0034] In the context of the invention, "C4 to C20 alkyl" means a linear or branched alkyl comprising 4 to 20 carbon atoms.

[0035] In the context of this invention, "alkenyl" means a linear or branched hydrocarbon radical comprising at least one double bond, said radical preferably comprising from 2 to 20 carbon atoms. Examples include propenyl and butenyl.

[0036] For the purposes of this invention, "alkynyl" means a linear or branched hydrocarbon radical comprising at least one triple bond, said radical preferably comprising from 2 to 20 carbon atoms. For the purposes of this invention, "aryl" means a monocyclic or bicyclic aromatic radical preferably comprising from 6 to 12 carbon atoms. Phenyl is an example.

[0037] In the context of this invention, "arylalkyl" means an alkyl group substituted by an aryl group, the arylalkyl group preferably comprising 7 to 20 carbon atoms. Benzyl is an example of an arylalkyl group.

[0038] In the context of the invention, "alkylaryl" means an aryl group substituted by an alkyl group, said alkylaryl group preferably comprising from 7 to 20 carbon atoms.

[0039] In the context of this invention, "heteroaryl" means a monocyclic or bicyclic aromatic radical comprising at least one heteroatom such as, for example, O, S, or N, and preferably comprising from 4 to 12 carbon atoms. Examples include furanyl, thiophenyl, pyrrolyl, pyridinyl, indolyl, and imidazolyl radicals.

[0040] In the context of the invention, "cycloalkyl" means a monocyclic or polycyclic system, preferably mono- or bicyclic, saturated, preferably comprising 3 to 12 carbon atoms, the rings being able to be fused or bridged in pairs, such as cyclopropyl, cyclopentyl, cyclohexyl or norbornyl groups.

[0041] In the context of the invention, "heterocycloalkyl" means a monocyclic or polycyclic system, preferably mono- or bicyclic, saturated, preferably comprising 3 to 12 carbon atoms and at least one heteroatom such as, for example, O or N, the rings being able to be fused or bridged in pairs.

[0042] In the context of the invention, "cycloalkenyl" means a monocyclic or polycyclic system, comprising at least one double bond, preferably comprising 3 to 12 carbon atoms, the rings being able to be fused or bridged in pairs.

[0043] In the context of the invention, "alkoxy" means an -O-alkyl radical.

[0044] Component A

[0045] Oxidizing

[0046] The oxidant can be chosen from the group consisting of: organic copper derivatives, iodoniums, thiopheniums, sulfoniums, thianthreniums, their derivatives, and mixtures thereof.

[0047] The oxidant is preferably chosen from the group consisting of:

[0048] compounds with the following formulas (la) or (Ib):

[0049]

[0050] (la) (lb)

[0051] in which:

[0052] each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R a , and R b represents, independently of each other, a radical chosen from the group consisting of a hydrogen atom, a halogen, an alkyl, a cycloalkyl or an aryl;

[0053] R f represents a perhaloalkyl or halogenoalkyl;

[0054] X' represents an anion;

[0055] - compounds with the following formulas: (Ha) or (llb) or (Ile):

[0056]

[0057] in which:

[0058] R 9 and R 10each represent, independently of each other, a hydrogen atom, an alkyl radical, an alkenyl radical, a cycloalkyl radical, a cycloalkenyl radical, an aryl radical, a chlorine atom, a bromine atom, an iodine atom, a carboxylic radical, or a -NO2 radical;

[0059] Z' represents a monovalent anion;

[0060] - W represents O or S;

[0061] - copper salts of formula (111-1) or a copper complex of formula (III-2):

[0062]

[0063] in which:

[0064] - R and R” each represent, independently of each other, an alkyl radical, a cycloalkyl radical, an aryl radical, a heteroaryl radical, said alkyl, cycloalkyl, aryl, heteroaryl radicals being possibly substituted by one or more halogen atoms such as for example by one or more fluorine atoms;

[0065] - R' represents a hydrogen atom, an alkyl radical, a cycloalkyl radical, an aryl radical, a heteroaryl radical,

[0066] or R and R' (or R' and R") can also be engaged in a single cycle comprising 5 to 8 carbon atoms, said cycle possibly comprising at least one heteroatom (such as for example O, S);

[0067] - R'” represents an alkyl radical, a cycloalkyl radical, an aryl radical, a heteroaryl radical, said alkyl, cycloalkyl, aryl, heteroaryl radicals possibly being substituted by one or more halogen atoms such as for example by one or more fluorine atoms;

[0068] - and their mixtures.

[0069] Compounds of formulas (la) or (Ib)

[0070] The anion X' can be chosen from the group consisting of FSOs', CF3SO3; CF2HSO3', Cl', Br, BF4-, BF3Cl-, PF6- and (F5Ph)4B-.

[0071] In the aforementioned formulas (a) or (Ib), R f may represent a haloalkyl. For example, it could be a fluoroalkyl radical, such as CHF2 or CH2F.

[0072] Preferably, in formulas (la) or (Ib), R f represents a perfluoroalkyl, and even more preferably CF3, C2F5, C3F7, C4F9. According to a particularly preferred mode, R f represents CF3.

[0073] The compound of formula (la) or (Ib) may be chosen from those in which: - each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 , R a and R b represents, independently of each other, a radical chosen from the group consisting of a hydrogen atom, a halogen, or an alkyl, preferably a hydrogen or a fluorine atom;

[0074] - R frepresents a perfluoroalkyl or a fluoroalkyl, preferably a perfluoroalkyl;

[0075] - X' represents an anion, preferably chosen from FSO3', CF3SO3 _ and BF4. Preferably, compounds of formula (la) are chosen from the group consisting of:

[0076]

[0077] Compounds of formula (la) can be prepared as described in WO 2016 / 107578. Compounds of formula (Ib) can be prepared as described in WO2011 / 013307.

[0078] Compounds with the formula (lia) or (Il b) or (Ile)

[0079] Preferably, in the aforementioned formulas (Ha), (llb) and (Ile), R 9 and R 10 each represents, independently of each other, an alkyl radical or a hydrogen atom.

[0080] In the aforementioned formulas (Ha), (llb), and (Ile), Z- can represent F-, Cl-, Br-, I-, NO3-, HSO4-, H2PO4-, HCOO-, CH3COO-, BF4-, AsF6-, PF6-, CH3-Ph-SO3-, (F5Ph)4B-, or SbF6-. Preferably, in the aforementioned formulas (Ha), (llb), and (Ile), Z- represents BF4 _ , PFe', CHs-Ph-SOs', (F5Ph)4B' or SbFe'. Even more preferably, Z- represents the (F5Ph)4B' anion with the following formula:

[0081]

[0082] Examples of iodonium salts with the formula (llb) include:

[0083]

[0084] Examples of iodonium salts with the formula (Ile) include:

[0085]

[0086] Examples of iodonium salts with formula (llb) include diphenyl iodonium hexafluorophosphate, diphenyl iodonium fluoroborate, diphenyl iodonium 2-carboxylate, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, 3,3'-dimethyl diphenyl iodonium hexafluorophosphate, and (4-Isopropylphenyl)(4-methylphenyl)iodonium tetrakis(pentafluorophenyl)borate.

[0087] Preferably, the iodonium salt is a salt of formula (llb). Even more preferably, the iodonium salt is (4-Isopropylphenyl)(4-methylphenyl)iodonium tetrakis(pentafluorophenyl)borate having the following formula:

[0088]

[0089] Organic copper derivative

[0090] Examples of copper salts of formula (III-1) include copper(II) acetate (e.g., anhydrous or monohydrate), copper(II) monofluoroacetate, copper(II) diffluoroacetate, copper(II) trifluoroacetate (e.g., anhydrous or monohydrate), copper(II) hexanoate, copper(II) ethyl-2-hexanoate, and mixtures thereof.

[0091] According to a preferred embodiment, in formula (III-1), R'” represents an alkyl radical having from 1 to 20 carbon atoms, preferably from 1 to 7 carbon atoms, said alkyl being optionally substituted by one or more halogen atoms such as, for example, by one or more fluorine atoms.

[0092] Examples of copper complexes with the formula (III-2) include copper(II) hexafluoroacetylacetonate (Cu(hfacac)2), copper(II) trifluoroacetylacetonate (Cu(tfacac)2), copper(II) acetylacetonate (Cu(acac)2), and copper(II) bis(2-acetylcyclohexanonate), which have the following formulas respectively:

[0093]

[0094] According to a preferred embodiment, in formula (III-2):

[0095] - R represents an alkyl radical, a cycloalkyl radical, an aryl radical, a heteroaryl radical, preferably an alkyl radical;

[0096] - R' represents a hydrogen;

[0097] - R” represents an alkyl radical possibly substituted by one or more halogen atoms, such as for example one or more fluorine atoms.

[0098] The organic copper derivative is preferably a copper complex of formula (III-2) and more particularly copper(II) acetylacetonate (Cu(acac)2).

[0099] The total oxidant content may range from 0.01% to 5% by weight, preferably from 0.01% to 2% by weight, and even more preferably from 0.01% to 1% by weight relative to the total weight of the crosslinkable two-component composition.

[0100] Preferably, the oxidant is chosen from among the copper salts of formula (111-1) or copper complex of formula (III-2) mentioned above, even more preferably copper(II) acetylacetonate (Cu(acac)2).

[0101] (meth)acrylate monomer

[0102] Component A comprises at least one (meth)acrylate monomer.

[0103] According to the invention, a "methacrylate monomer" is understood to mean a monomer comprising a methacrylate group. According to the invention, the term "methacrylate" includes acrylate groups (-O-CO-CH=CH2) and methacrylate groups (-O-CO-C(CH3)=CH2).

[0104] The (meth)acrylate monomer can have a molecular weight ranging from 100 to 1000 g / mol, preferably from 100 to 500 g / mol.

[0105] The (meth)acrylate monomer may comprise a mixture of (meth)acrylate monomers having different functionalities. For example, the (meth)acrylate monomer may comprise a mixture of a (meth)acrylate monomer containing a single acrylate or methacrylate group per molecule (referred to herein as "mono-(meth)acrylate monomer"), and a monomer containing 2 or more, preferably 2 or 3, acrylate and / or methacrylate groups per molecule.

[0106] Mono-(meth)acrylate monomers may be selected from the group consisting of mono-(meth)acrylate esters of aliphatic alcohols (in which the aliphatic alcohol may be straight-chain, branched-chain or alicyclic and may be a mono-alcohol, a di-alcohol or a polyalcohol, provided that only one hydroxyl group is esterified with (meth)acrylic acid); mono-(meth)acrylate esters of aromatic alcohols (such as phenols, including alkylated phenols); mono-(meth)acrylate esters of alkylaryl alcohols (such as benzyl alcohol); mono-(meth)acrylate esters of oligomeric and polymeric glycols such as diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol and polypropylene glycol); mono-(meth)acrylate esters of monoalkyl ethers of glycols and oligoglycols;mono-(meth)acrylate esters of alkoxylated aliphatic alcohols (e.g., ethoxylated and / or propoxylated) (in which the aliphatic alcohol may be straight-chain, branched-chain, or alicyclic and may be a mono-alcohol, a di-alcohol, or a polyalcohol, provided that only one hydroxyl group of the alkoxylated aliphatic alcohol is esterified with (meth)acrylic acid); mono-(meth)acrylate esters of alkoxylated aromatic alcohols (e.g., ethoxylated and / or propoxylated) (such as alkoxylated phenols); mono-(meth)acrylates of caprolactone; and mixtures thereof.

[0107] Specific examples of mono-(meth)acrylate monomers are chosen from the group consisting of methyl methacrylate; ethyl (meth)acrylate; n-propyl (meth)acrylate; n-butyl (meth)acrylate; isobutyl (meth)acrylate; sec-butyl (meth)acrylate; tert-butyl (meth)acrylate; n-hexyl (meth)acrylate; 2-ethylhexyl (meth)acrylate; n-octyl (meth)acrylate; isooctyl (meth)acrylate; n-decyl (meth)acrylate; n-dodecyl (meth)acrylate; tridecyl (meth)acrylate; tetradecyl (meth)acrylate; hexadecyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate; 2- and 3-hydroxypropyl (meth)acrylate; 2-methoxyethyl (meth)acrylate; 2-ethoxyethyl (meth)acrylate; 2- and 3-ethoxypropyl (meth)acrylate; tetrahydrofurfuryl (meth)acrylate; alkoxylated tetrahydrofurfuryl (meth)acrylate; 2-(2-ethoxyethoxy)ethyl (meth)acrylate; cyclohexyl (meth)acrylate; glycidyl (meth)acrylate; isodecyl (meth)acrylate;lauryl (meth)acrylate; 2-phenoxyethyl (meth)acrylate; alkoxylated phenol (meth)acrylates; alkoxylated nonylphenol (meth)acrylates; cyclic trimethylolpropane (meth)acrylate formal; glycerol (meth)acrylate carbonate; glycerol (meth)acrylate formal; hydroxyethyl (meth)acrylate; isobornyl (meth)acrylate; tricyclodecanemethanol (meth)acrylate; tert-butylcyclohexanol (meth)acrylate; trimethylcyclohexanol (meth)acrylate; diethylene glycol monomethyl ether (meth)acrylate; benzyl (meth)acrylate; diethylene glycol monoethyl ether (meth)acrylate; diethylene glycol monobutyl ether (meth)acrylate; triethylene glycol monoethyl ether (meth)acrylate; ethoxylated lauryl (meth)acrylate; (Meth)acrylates of methoxy polyethylene glycol; (Meth)acrylates of 3-(2-hydroxyalkyl)oxazolidinone; and mixtures thereof.

[0108] Suitable (meth)acrylate monomers containing two or more (meth)acrylate groups per molecule may include acrylate and methacrylate esters of polyols. Examples of suitable polyols include ethylene glycol, 1,2- or 1,3-propylene glycol, 1.2-, 1,3- or 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, 2.2-diethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 3,3-dimethyl-1,5-pentanediol, neopentyl glycol, 2,4-diethyl-1,5-pentanediol, 3,3-butylethyl-1,5-pentane diol, cyclohexanediol, cyclohexane-1,4-dimethanol, norbornene dimethanol, norbornane dimethanol, tricyclodecanediol, tricyclodecane dimethanol, dicyclopentadiene diol, hydroquinone bis(2-hydroxyethyl) ether, pyrocatechol, resorcinol, cardol, phloroglucinol, pyrogallol, tris(hydroxyphenyl)methane, tris(hydroxyphenyl)ethane, bisphenol A, B, F or S, hydrogenated bisphenol A, B, F or S,trimethylolmethane, trimethylolethane, triméthylolpropane, di(trimethylolpropane), triethylolpropane, pentaerythritol, di(pentaerythritol), glycerol, di-, tri- ou tetraglycerol, un polyglycerol, di-, tri- ou tetra(ethylene glycol), di-, tri- ou tetra(1,2-propylene glycol), di-, tri- ou tetra(1,3-propylene glycol), di-, tri- ou tetra(1,4-butylene glycol), un poly(ethylene glycol), un poly(propylene glycol), un poly(trimethylene glycol), un poly(tetramethylene glycol), un poly(ethylene glycol-co-propylene glycol), un alditol (i.e. erythritol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, galactitol, fucitol or iditol), un dianhydrohexitol (i.e. isosorbide, isomannide, isoidide), tris(2-hydroxyethyl)isocyanurate, un C, 36diol dimers, polybutadiene polyols, polyester polyols, polyether polyols, polyorganosiloxane polyols, polycarbonate polyols, and their alkoxylated (e.g., ethoxylated) derivatives. Such polyols may be fully or partially esterified (with (meth)acrylic acid, (meth)acrylic anhydride, (meth)acryloyl chloride, or other), provided they contain at least two (meth)acrylate functional groups per molecule.

[0109] Examples of (meth)acrylate monomers containing two or more (meth)acryloyloxy groups per molecule may include bisphenol A di(meth)acrylate; hydrogenated bisphenol A di(meth)acrylate; ethylene glycol di(meth)acrylate; diethylene glycol di(meth)acrylate; triethylene glycol di(meth)acrylate; tetraethylene glycol di(meth)acrylate; polyethylene glycol di(meth)acrylate; propylene glycol di(meth)acrylate; dipropylene glycol di(meth)acrylate; tripropylene glycol di(meth)acrylate; tetrapropylene glycol di(meth)acrylate; polypropylene glycol di(meth)acrylate; polytetramethylene glycol di(meth)acrylate; 1,2-butanediol di(meth)acrylate; 2,3-butanediol di(meth)acrylate; 1,3-butanediol di(meth)acrylate; 1,4-butanediol di(meth)acrylate; 1,5-pentanediol di(meth)acrylate; 1,6-hexanediol di(meth)acrylate; 1,8-octanediol di(meth)acrylate; 1,9-nonanediol di(meth)acrylate; 1,10-nonanediol di(meth)acrylate;1,12-dodecanediol di(meth)acrylate; neopentyl glycol di(meth)acrylate; 2-methyl-2,4-pentanediol di(meth)acrylate; polybutadiene di(meth)acrylate; cyclohexane-1,4-dimethanol di(meth)acrylate; tricyclodecane and dimethanol di(meth)acrylate; metallic di(meth)acrylates; modified metallic di(meth)acrylates; glyceryl di(meth)acrylate; glyceryl tri(meth)acrylate; trimethylolethane tri(meth)acrylate; trimethylolethane di(meth)acrylate; trimethylolpropane tri(meth)acrylate; trimethylolpropane di(meth)acrylate; pentaerythritol di(meth)acrylate; pentaerythritol tri(meth)acrylate; pentaerythritol tetra(meth)acrylate; di(trimethylolpropane) diacrylate; di(trimethylolpropane) triacrylate; di(trimethylolpropane) tetraacrylate, sorbitol penta(meth)acrylate; di(pentaerythritol)tetraacrylate; di(pentaerythritol) pentaacrylate; di(pentaerythritol)hexa(meth)acrylate;tri(meth)acrylate of tris (2-hydroxyethyl) isocyanurate; as well as their alkoxylated derivatives (e.g., ethoxylated and / or propoxylated); and mixtures thereof.

[0110] The (meth)acrylate monomer can be a recycled or non-recycled monomer.

[0111] The (meth)acrylate monomer can be partially or totally bio-based.

[0112] Preferably, component A comprises one or more mono-(meth)acrylate monomers.

[0113] Even more preferably, component A comprises lauryl (meth)acrylate, hydroxyethyl methacrylate, or mixtures thereof.

[0114] The total content of (meth)acrylate monomer(s) in component A can range from 2% to 20% by weight, preferably from 5% to 15% by weight relative to the total weight of said component A. The content of (meth)acrylate monomer(s) in the crosslinkable two-component composition according to the invention can range from 2% to 20% by weight, preferably from 4% to 17%, even more preferably from 5% to 15% by weight relative to the total weight of said crosslinkable two-component composition.

[0115] Halogenated carboxylic acid (optional)

[0116] Component A may further comprise a halogenated carboxylic acid.

[0117] The halogenated carboxylic acid can be chosen from monohalogenated (containing one halogen atom), dihalogenated (containing two halogen atoms) or trihalogenated (containing three halogen atoms) carboxylic acids.

[0118] The halogenated carboxylic acid may be chosen from the group consisting of monochloroacetic acid, monofluoroacetic acid, dichloroacetic acid, difluoroacetic acid, trichloroacetic acid, trifluoroacetic acid, and mixtures thereof.

[0119] Preferably, the halogenated carboxylic acid is chosen from dichloroacetic acid, difluoroacetic acid and mixtures thereof.

[0120] When present, the total content of halogenated carboxylic acid(s) can range from 0.1% to 10% by weight, preferably from 0.15% to 5% by weight, and even more preferably from 0.2% to 1% by weight relative to the total weight of the crosslinkable two-component composition.

[0121] Polymers / oligomers (meth)acrylate (optional)

[0122] The composition may include at least one oligomer (meth)acrylate or one polymer (meth)crylate.

[0123] The (meth)acrylate oligomer can comprise 1 to 18 (meth)acrylate groups, in particular 2 to 6 (meth)acrylate groups, more particularly 2 to 6 acrylate groups.

[0124] The oligomer (meth)acrylate may have a number-average molecular mass greater than 1000 g / mol, and preferably from more than 1000 g / mol to 15,000 g / mol, more particularly from more than 1000 g / mol to 5000 g / mol.

[0125] In particular, (meth)acrylate oligomers can be selected from the group consisting of urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyether (meth)acrylate oligomers, polydiene (meth)acrylate oligomers, polycarbonate (meth)acrylate oligomers, polyester (meth)acrylate oligomers, and mixtures thereof. Examples of polyester (meth)acrylate oligomers include the reaction products of acrylic or methacrylic acid, or their mixtures, with polyester polyols terminated by a hydroxyl group. The reaction process can be carried out in such a way that all or virtually all of the hydroxyl groups of the polyester polyol have been (meth)acrylated, particularly in cases where the polyester polyol is difunctional.Polyester polyols can be prepared by polycondensation reactions of polyols (especially diols) and polycarboxylic acid functional compounds (especially dicarboxylic acids and anhydrides). Both the polyol and polycarboxylic acid functional compounds can have linear, branched, cycloaliphatic, or aromatic structures and can be used individually or in mixtures.

[0126] Examples of suitable epoxy(meth)acrylates include the reaction products of acrylic or methacrylic acid or their mixtures with an epoxy resin (polyglycidyl ether or ester). The epoxy resin may include, in particular, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, novolac epoxy resin, and hydrogenated bisphenol. Diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-1,4-dioxane, bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexanecarboxylate, dicyclopentadiene diepoxide,1,4-Butanediol diglycidyl ether, 1,6-Hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polyglycidyl ethers of a polyether polyol obtained by the addition of one or more alkylene oxides to an aliphatic polyhydric alcohol such as ethylene glycol, propylene glycol and glycerol, diglycidyl esters of aliphatic dibasic acids in C6-C22, glycidyl esters of C30-36 fatty acid dimers, epoxidized vegetable oil (such as epoxidized soybean oil and epoxidized linseed oil), epoxidized polybutadiene, and the like.

[0127] Suitable polyether (meth)acrylate oligomers include, but are not limited to, the condensation reaction products of acrylic or methacrylic acid or their mixtures with polyetherols that are polyether polyols (such as polyethylene glycol, polypropylene glycol, or polytetramethylene glycol). Suitable polyetherols may be linear or branched substances containing ether bonds and terminal hydroxyl groups. Polyetherols may be prepared by ring-opening polymerization of cyclic ethers such as tetrahydrofuran or alkylene oxides (e.g., ethylene oxide and / or propylene oxide) with a starting molecule. Suitable starting molecules include water, polyhydroxyl functional materials, polyester polyols, and amines.

[0128] Polyurethane (meth)acrylate oligomers (sometimes also referred to as 'urethane (meth)acrylate oligomers') suitable for use in Composition A include, in particular, urethanes based on aliphatic, cycloaliphatic and / or aromatic polyester-polyols and polyether-polyols and aliphatic, cycloaliphatic and / or aromatic polyester diisocyanates and polyether diisocyanates capped with (meth)acrylate terminal groups.

[0129] Polyurethane (meth)acrylate oligomers can be prepared by reacting aliphatic, cycloaliphatic and / or aromatic polyisocyanates (e.g., diisocyanate, triisocyanate) with OH-terminated polyester polyols, polyether polyols, polycarbonate polyols, polycaprolactone polyols, polyorganosiloxane polyols (e.g., polydimethylsiloxane polyols), or polydiene polyols (e.g., polybutadiene polyols), or combinations thereof to form isocyanate-functionalized oligomers which are then reacted with hydroxyl-functionalized (meth)acrylates (such as 2-hydroxyethyl (meth)acrylate or 3-hydroxypropyl (meth)acrylate) to provide terminal (meth)acrylate groups. For example, polyurethane (meth)acrylate oligomers may contain two, three, four or more (meth)acrylate functional groups per molecule.Other addition orders can also be used to prepare polyurethane (meth)acrylate, as is known in the technique. For example, hydroxyl-functionalized (meth)acrylate can first be reacted with a polyisocyanate to obtain isocyanate-functionalized (meth)acrylate, which can then be reacted with an OH-terminated polyester-polyol, a polyether polyol, a polycarbonate polyol, a polycaprolactone polyol, polydimethylsiloxane polyol, polybutadiene polyol, or a combination thereof. Alternatively, all components can be combined and reacted simultaneously.

[0130] Oligomers of this type are also marketed by Arkema.

[0131] Component A preferably comprises a polyurethane (meth)acrylate oligomer, preferably having a functionality equal to 2.

[0132] The total content of oligomer(s) and / or polymer(s) (meth)acrylate in component A may range from 2 to 10% by weight, preferably from 5 to 10% by weight relative to the total weight of said component A. The content of oligomer(s) and / or polymer(s) (meth)acrylate in the crosslinkable two-component composition according to the invention may range from 2 to 10% by weight, preferably from 5% to 10% by weight relative to the total weight of said crosslinkable two-component composition.

[0133] Photo-initiator P1 (optional)

[0134] Component A may further include a photoinitiator P1.

[0135] The photoinitiator can be any photoinitiator known to those skilled in the art. Under the influence of UV-visible radiation, the photoinitiator typically generates radicals that initiate the photopolymerization reaction, thereby increasing its efficiency. It is, of course, chosen according to the light source used, based on its ability to efficiently absorb the selected radiation. For example, the appropriate photoinitiator can be chosen based on its UV-visible absorption spectrum. Advantageously, the photoinitiator is suitable for use with irradiation sources emitting in the near-field range of 300 to 420 nm. Advantageously, the UV or visible radiation source can be an LED.

[0136] The photoinitiator P1 can be chosen from the group consisting of:

[0137] - Type I photoinitiators selected from:

[0138] - the family of acetophenones and alkoxyacetophenones, such as for example 2,2-dimethoxy-2-phenylacetophenone and 2-diethyl-2-phenylacetophenone;

[0139] - the hydroxyacetophenone family, such as for example 2,2-dimethyl-2-hydroxyacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methyl-propriophenone and 2-hydroxy-4'-(2-hydroxypropoxy)-2-methyl-propriophenone;

[0140] - the alkylaminoacetophenone family, such as for example 2-methyl-4'-(methylthio)-2-morpholino-propriophenone, 2-benzyl-2-(dimethylamino)-4-morpholinobutyrophenone and 2-(4-(methylbenzyl)-2-(dimethylamino)-4-morpholino-butyrophenone;

[0141] - the family of benzoin ethers, such as for example benzyl, methyl benzoin ether and isopropyl benzoin ether;

[0142] - the family of phosphine oxides, such as for example diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), ethyl-(2,4,6-trimethylbenzoyl)phenylphosphine oxide (TPO-L) and bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylphenyl phosphine oxide (BAPO); - the family of metallocenes, such as for example ferrocene, bis(eta 5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro)-3-(1H-pyrrole-1-yl)-phenyl) titanium and iron (cumene)cyclopentadienyl hexafluorophosphate;

[0143] - Type II photoinitiators selected from:

[0144] - the benzophenone family, such as for example 4-phenylbenzophenone, 4-(4'-methylphenylthio)benzophenone, 1-[4[ (4-benzoylphenyl)thio]phenyl]- 2-methyl-2-[(4-methylphenyl)sulfonyl]-1 -propanone;

[0145] - the thioxanthone family, such as for example isopropylthioxanthone (ITX), 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2-chlorothioxanthone and 1-chloro-4-isopropylthioxanthone;

[0146] - the family of benzoyl formate esters, such as methylbenzoyl formate;

[0147] - the dibenzylidene ketone family, such as for example p-dimethylaminoketone;

[0148] - the coumarin family, such as for example 5-methoxy and 7-methoxy coumarin, 7-diethylamino coumarin and N-phenyleglycine coumarin; - photoinitiators of the dye family such as for example triazines, fluorones, cyanines, safranins, 4,5,6,7-tetrachloro-3',6'-dihydroxy-2',4',5',7'-tetraiodo-3H-spiro[isobenzofuran-1,9'-xanthen]-3-one, pyrylium and thiopyrylium, thiazines, flavins, pyronines, oxazines, rhodamines; - and mixtures thereof.

[0149] According to a preferred embodiment, the photoinitiator P1 is selected from:

[0150] - the family of phosphine oxides, such as for example diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), ethyl-(2,4,6-trimethylbenzoyl)phenylphosphine oxide (TPO-L) and bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylphenyl phosphine oxide (BAPO);

[0151] - the thioxanthone family, such as for example isopropylthioxanthone (ITX), 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2-chlorothioxanthone and 1-chloro-4-isopropylthioxanthone;

[0152] the photoinitiator P1 being even more preferentially chosen from diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), and ethyl-(2,4,6-trimethylbenzoyl)phenylphosphine oxide (TPO-L).

[0153] The total content of photoinitiator P1 may range from 0% to 5% by weight, preferably from 0% to 2% by weight, and even more preferably from 0% to 1% by weight relative to the total weight of the crosslinkable two-component composition according to the invention. If present in the two-component composition according to the invention, the photoinitiator content may be greater than or equal to 0.01%, for example, greater than or equal to 0.1% by weight relative to the total weight of said composition.

[0154] Component B

[0155] Reducing agent

[0156] Component B includes a reducer.

[0157] The reducing agent is preferably chosen from the group consisting of polyamines, dihydropyridine compounds, sulfinates, aromatic phosphines, and mixtures thereof.

[0158] Polyamines

[0159] Polyamines can be chosen from:

[0160] - polyamines comprising at least one primary amine group (-NH2) (B1);

[0161] - polyamines not including a primary amine group (-NH2) (B2).

[0162] Examples of polyamines containing at least one primary amine group (B1) include:

[0163] (i) primary aliphatic, cycloaliphatic or arylaliphatic diamines, such as, for example, ethylenediamine (EDA); 2,2-dimethyl-1,3-propanediamine; 1,3-pentanediamine (DAMP); 1,5-pentanediamine; 1,5-diamino-2-methylpentane (MPMD); 2-butyl-2-ethyl-1,5-pentanediamine (C11-neodiamine); 4,4'-diaminodicyclohexyl methane; 2,4'-diaminodicyclohexyl methane; 4,4' methylene bis(2-methylcyclohexanamine; 1,6-hexanediamine (hexamethylenediamine, HMDA); 2,5-dimethyl-1,6-hexanediamine; 2,2,4- and / or 2,4,4-trimethylhexamethylenediamine; 1,7-heptanediamine; 1,8-octanediamine; 1,9-nonanediamine; 1,10-decanediamine; 1,11-undecanediamine; 1,12-dodecanediamine; 1,2-, 1,3- and 1,4-diaminocyclohexane; bis(4-aminocyclohexyl)methane; bis(4-amino-3-methylcyclohexyl)methane; bis(4-amino-3-ethylcyclohexyl)methane; bis(4-amino-3,5-dimethylcyclohexyl)methane; bis(4-amino-3-ethyl-5-methylcyclohexyl)methane; 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isophorone diamine, I PDA);2- and / or 4-methyl-1,3-diaminocyclohexane; 1,3-bis(aminomethyl)-cyclohexane; 1,4-bis(aminomethyl)cyclohexane; 2,5(2,6)-bis(aminomethyl)-bicyclo[2.2.1]heptane (norboranediamine, NBDA); 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0<2,6>]-decane (TCD-diamine); 1,4-diamino-2,2,6-trimethylcyclohexane (TMCDA); 1,8-menthanediamine; 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]undecane; 1,3-bis(aminomethyl)benzene (m-XDA) and mixtures thereof; ii) primary diamines comprising at least one secondary amine group (-NHR, with R different from H) such as, for example, 3-(2-aminoethyl)aminopropylamine, bis(hexamethylene)triamine (BHMT); diethylenetriamine (DETA); triethylenetetramine (TETA); tetraethylenepentamine (TEPA); pentaethylenehexamine (PEHA); and mixtures thereof;

[0164] iii) aromatic polyamines such as, for example, 2,4-tolylenediamine (2,4-TDA); 2,6-tolylenediamine (2,6-TDA); m-phenylenediamine (PDA); 4,4'-diaminodiphenylmethane (4,4'-MDA); 2,4'-diaminodiphenylmethane (2,4'-MDA); and mixtures thereof;

[0165] (iv) polyamines comprising a tertiary amine group (-NR2, R being different from H) and at least two primary amine groups (-NH2) such as, for example, N,N'-bis(aminopropyl)piperazine; N,N-bis(3-aminopropyl)methylamine; N,N-bis(3-aminopropyl)ethylamine; N,N-bis(3-aminopropyl)propylamine; N,N-bis(3-aminopropyl)cyclohexylamine; N,N-bis(3-aminopropyl)-2-ethylhexylamine; tris(2-aminoethyl)amine; tris(2-aminopropyl)amine; tris(3-aminopropyl)amine; and mixtures thereof;

[0166] (v) polyetheramines, in particular polyetherdiamines such as, for example, bis(2-aminoethyl)ether; 3,6-dioxaoctane-1,8-diamine; 4,7-dioxadecane-1,10-diamine; 4,7-dioxadecane-2,9-diamine; 4,9-dioxadodecane-1,12-diamine; 5,8-dioxadodecane-3,10-diamine; 4,7,10-trioxatridecane-1,13-diamine; bis(3-aminopropyl)polytetrahydrofurans; and mixtures thereof;

[0167] (vi) Polyamines comprising a primary amine group (-NH2) and a secondary amine group (-NHR, R being different from H) such as, for example, N-butyl-1,2-ethanediamine; N-hexyl-1,2-ethanediamine; N-cyclohexyl-1,2-ethanediamine; 4-aminomethylpiperidine; N-(2-aminoethyl)piperazine; N-methyl-1,3-propanediamine; N-butyl-1,3-propanediamine; N-(2-ethylhexyl)-1,3-propanediamine; N-cyclohexyl-1,3-propanediamine; 3-methylamino-1-pentylamine; 3-ethylamino-1-pentylamine; 3-cyclohexylamino-1-pentylamine; and mixtures thereof;

[0168] vii) amino alcohols such as, for example, aminoethylethanolamine (AEEA); viii) polyamidoamines;

[0169] ix) fatty amines, dimers or trimers;

[0170] x) polyethyleneimines (and their dendrimers) such as, for example, those having a number-average molecular mass (Mn) ranging from 450 to 25000 g / mol and having in particular at least one radical of the following formula:

[0171]

[0172] (for example, we can mention polyethyleneimines marketed under the name "LUPASOL" marketed by BASF);

[0173] xi) polypropyleneimines (and their dendrimers);

[0174] xii) poly(propylene-ethylene)imines;

[0175] xiii) and their mixtures.

[0176] Polyamines (B1) are preferably chosen from:

[0177] i) primary aliphatic, cycloaliphatic or arylaliphatic diamines;

[0178] ii) primary diamines comprising at least one secondary amine group (-NHR, with R different from H);

[0179] x) polyethyleneimines (and their dendrimers);

[0180] and their mixtures.

[0181] Among the polyamines not comprising a primary amine group (B2), we can cite for example the polyamines comprising one or more secondary amine groups (-NHR, R being different from H) and / or one or more tertiary amine groups (-NR2, R being different from H).

[0182] B2 polyamines can be selected from the group consisting of N,N,N',N'-tetraalkyl alkylenediamines, such as, for example, N,N,N',N'-tetramethylethylenediamine (TEMED, CAS No. 110-18-9), N,N,N',N'-tetramethyl-2,2'-oxybis(ethylamine) (CAS No. 3033-62-3), N,N,N',N'-tetramethyltrimethylenediamine (CAS No. 110-95-2) and N,N,N',N'-tetramethylhexamethylenediamine (CAS No. 111-18-2).

[0183] Dihydropyridine compound

[0184] Dihydropyridine compounds are preferably chosen from the dihydropyridines of the following formulas (VI) to (X):

[0185]

[0186] in which:

[0187] each of R 11 to R 17 represents, independently of each other, a hydrogen, an alkyl, an alkenyl, an alkynyl, a cycloalkyl, a heterocycloalkyl, a heteroaryl, an aryl, an alkylaryl, an arylalkyl, a -COOR radical C ;

[0188] said alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, heteroaryl, aryl, alkylaryl, arylalkyl groups being possibly substituted;

[0189] and R c representing an alkyl or aryl radical;

[0190] or two radicals from among R 11 to R 17 together form a mono- or polycyclic cycle, possibly substituted.

[0191] The dihydropyridine compound may be chosen from those of formulas (VI) to (X) in which:

[0192] R 17 represents an aryl or heteroaryl, said aryl or heteroaryl being possibly substituted, and

[0193] of R 11 to R 16 represents, independently of each other, a hydrogen, an alkyl, an alkenyl, an alkynyl, a cycloalkyl, a heterocycloalkyl, a heteroaryl, an aryl, an alkylaryl, an arylalkyl, a -COOR radical a , R a representing an alkyl;

[0194] R 11 to R 16 representing preferably independently of each other, a hydrogen or an alkyl or a -COOR radical C with R c representing an alkyl group. The dihydropyridine compound is preferably chosen from the following compounds:

[0195]

[0196] Dihydropyridines may be commercially available such as, for example, Vanax 808 HP marketed by VANDERBILT CHEMICALS, or may be synthesized as described, for example, in WO 2006 / 086602.

[0197] Sulfinates

[0198] Sulfinates preferably have the following formula (XI):

[0199] [R a -SO2-] P Q P+ (XI)

[0200] in which:

[0201] - R a represents an aryl or heteroaryl radical, said heteroaryl and aryl being possibly substituted by at least one of the following radicals: F, OH, C(O)OMe, NHC(O)Me, methyl (Me), CF3, OH or SO2-;

[0202] - Q represents Li, Na, K or Zn, preferably Na or K;

[0203] - p represents 1 or 2.

[0204] The compound with formula (XI) is preferably chosen from the following compounds:

[0205]

[0206] According to a preferred embodiment, the compound of formula (XI) is chosen from the following compounds:

[0207]

[0208] Aromatic phosphines

[0209] Preferably, aromatic phosphines are chosen from those having one of the following formulas (C) or (D):

[0210]

[0211] in which:

[0212] - each of Ar1, Ar2, Ar3, Ar4 represents, independently of each other, an aryl or possibly substituted heteroaryl;

[0213] - each of R 18 , R 19 , represents, independently of each other, an organic radical. The substituents are preferably chosen from the group consisting of: an alkoxy (preferably -OCH3), an alkyl (preferably methyl or tert-butyl), -COOH, -O-phenyl-P(Phenyl)2, -P(Phenyl)2.

[0214] In formula (C) above:

[0215] - R 19preferably represents an alkyl, a cycloalkyl, an aryl, a heteroaryl, an arylalkyl, said alkyl, cycloalkyl, aryl, heteroaryl, arylalkyl being optionally substituted, R 19 representing even more preferentially a possibly substituted aryl;

[0216] And / or

[0217] - Ar2 preferably represents one of the following groups:

[0218]

[0219] And / or

[0220] - An preferably represents one of the following groups:

[0221]

[0222] Preferably, in formula (C) above, R 19 represents one of the following groups:

[0223]

[0224] In formula (D) above: - R 18preferably represents an alkyl, a cycloalkyl, an aryl, a heteroaryl, an arylalkyl, said alkyl, cycloalkyl, aryl, heteroaryl, arylalkyl being optionally substituted. Even more preferably R 18 represents a possibly substituted aryl; And / or

[0225] - Ar4 preferably represents one of the following groups:

[0226]

[0227] And / or

[0228] - Ara preferably represents one of the following groups:

[0229]

[0230] Preferably, in formula (D) above, R 18 represents one of the following groups:

[0231]

[0232] Preferably, the compound with formula (C) is chosen from the group consisting of:

[0233]

[0234] Preferably, the compound with formula (D) is chosen from the group consisting of:

[0235]

[0236] Preferably, when the oxidant in component A is chosen from compounds of formula (la), (Ib), (Ha), (llb) or (Ile), then the reducer of component B is chosen from polyamines, dihydropyridine compounds, aromatic phosphines, as defined above.

[0237] Preferably, when the oxidant in component A is chosen from copper salts of formula (111-1) or a copper complex of formula (III-2), then the reducer of component B is chosen from sulfinates as defined above.

[0238] Preferred compositions according to the invention are those in which: - the oxidant of component A is chosen from copper salts of formula (III-1) or copper complexes of formula (III-2), preferably the oxidant is copper(II) acetylacetonate; and

[0239] - the reducing agent of component B is chosen from among the sulfinates of formula (XI) as defined above, preferably those chosen from:

[0240]

[0241] The total content of reducer can range from 0.1% to 5% by weight, preferably from 0.1% to 3% by weight, and even more preferably from 0.1% to 1% by weight relative to the total weight of the crosslinkable two-component composition according to the invention.

[0242] (meth)acrylate monomer

[0243] Component B may comprise at least one (meth)acrylate monomer. Preferably, component B comprises at least one.

[0244] The (meth)acrylate monomer is in particular as defined above for component A. Preferably, the (meth)acrylate monomer of component B does not include a labile proton (such as, for example, a COOH or OH group).

[0245] Preferably, component B comprises one or more mono-(meth)acrylate monomers, more preferably selected from methyl methacrylate; ethyl (meth)acrylate; n-propyl (meth)acrylate; n-butyl (meth)acrylate; isobutyl (meth)acrylate; sec-butyl (meth)acrylate; tert-butyl (meth)acrylate; n-hexyl (meth)acrylate; 2-ethylhexyl (meth)acrylate; n-octyl (meth)acrylate; isooctyl (meth)acrylate; n-decyl (meth)acrylate; n-dodecyl (meth)acrylate; tridecyl (meth)acrylate; tetradecyl (meth)acrylate; hexadecyl (meth)acrylate; 2-methoxyethyl (meth)acrylate; 2-ethoxyethyl (meth)acrylate; 2- and 3-ethoxypropyl (meth)acrylate; tetrahydrofurfuryl (meth)acrylate; alkoxylated tetrahydrofurfuryl (meth)acrylate; 2-(2-ethoxyethoxy)ethyl (meth)acrylate; cyclohexyl (meth)acrylate; glycidyl (meth)acrylate; isodecyl (meth)acrylate; lauryl (meth)acrylate;2-Phenoxyethyl (meth)acrylate; alkoxylated phenol (meth)acrylates; alkoxylated nonylphenol (meth)acrylates; isobornyl (meth)acrylate; diethylene glycol monomethyl ether (meth)acrylate; benzyl (meth)acrylate; ethoxylated lauryl (meth)acrylate; polyethylene glycol methoxy (meth)acrylates; 3-(2-hydroxyalkyl)oxazolidinone (meth)acrylates; and mixtures thereof.

[0246] More preferably, component B comprises benzyl (meth)acrylate. The total content of (meth)acrylate monomer(s) in component B may range from 5 to 20% by weight, preferably from 8 to 15% by weight relative to the total weight of said component B.

[0247] Polymers / oligomers (meth)acrylate (optional)

[0248] Component B may comprise at least one (meth)acrylate oligomer or (meth)crylate polymer. Preferably, component B comprises at least one.

[0249] The oligomer (meth)acrylate or the polymer (meth)crylate is in particular as defined above for component A.

[0250] Component B preferably comprises a polyurethane (meth)acrylate oligomer, preferably having a functionality equal to 2.

[0251] The total content of oligomer(s) and polymer(s) (meth)acrylate in component B may range from 5 to 15% by weight, preferably from 5 to 12% by weight relative to the total weight of said component B.

[0252] Composition

[0253] Thermally conductive charge

[0254] The composition according to the invention comprises at least one thermally conductive filler in component A and / or B.

[0255] The thermally conductive charge typically allows heat to be diffused thanks to its thermal conductivity value.

[0256] Preferably, the thermally conductive load has a thermal conductivity greater than or equal to 5 W / mK, preferably greater than or equal to 10 W / mK, more preferably greater than or equal to 20 W / mK.

[0257] The thermal conductivity of the conductive load can be determined by any method known to a person skilled in the art. Advantageously, the thermal conductivity is determined according to ASTM D5470-17.

[0258] The thermally conductive filler can be chosen from aluminosilicates, aluminum nitride, boron nitride, metal oxides (such as zinc oxide, magnesium oxide, beryllium oxide, titanium oxide, nickel oxide, copper oxide, tin oxide, or aluminum oxide), metal hydroxides (such as aluminum hydroxide (also called ATH or aluminum trihydroxide, with the formula Al(OH)3), cadmium hydroxide (Cd(OH)2), lead(II) hydroxide (Pb(OH)2), zinc hydroxide (Zn(OH)2), beryllium hydroxide (Be(OH)2), magnesium hydroxide (Mg(OH)2), calcium hydroxide (Ca(OH)2), strontium hydroxide (Sr(OH)2), hydroxide of barium (Ba(OH)2), iron hydroxides), metals (such as copper), carbon black, and mixtures thereof.

[0259] Examples of iron hydroxides include iron(II) hydroxide (Fe(OH)2), iron(III) hydroxide (Fe(OH)3), iron(III) oxyhydroxide (FeO(OH)) and mixtures thereof.

[0260] Preferably, the thermally conductive charge is chosen from metal oxides, metal hydroxides, and mixtures thereof.

[0261] Even more preferentially, the thermally conductive charge is chosen from aluminum oxides, aluminum hydroxides, and their mixtures.

[0262] The thermally conductive charge is preferably of natural origin (i.e., it is not synthetic).

[0263] Preferably, the thermally conductive charge has a density at 23°C ranging from 2 to 6, preferably from 2 to 5.

[0264] Advantageously, the total content of thermally conductive filler(s) in component A ranges from 50% to 90% by weight relative to the total weight of component A, preferably from 60% to 87% by weight, more preferably from 65% to 85% by weight, and even more preferably from 70% to 80% by weight.

[0265] Advantageously, the total content of thermally conductive filler(s) in component B ranges from 50% to 90% by weight relative to the total weight of component B, preferably from 60% to 87% by weight, more preferably from 65% to 85% by weight, and even more preferably from 70% to 80% by weight.

[0266] According to a preferred embodiment, each of the components A and B includes at least one thermally conductive load.

[0267] Advantageously, the total content of thermally conductive filler(s) in the total composition ranges from 50% to 95% by weight, preferably from 60% to 90% by weight, and even more preferably from 65% to 85% by weight.

[0268] Advantageously, the composition comprises at least 60% by weight of aluminum hydroxide relative to the total weight of all thermally conductive fillers, preferably at least 80% by weight, and even more preferably the composition comprises 100% aluminum hydroxide as thermally conductive fillers. The thermally conductive filler preferably has a particle size (d50) ranging from 2 to 50 microns.

[0269] The d50 particle size is well known to those skilled in the art as the maximum size of 50% of the smallest particles by volume, and can be measured with a particle size analyzer, in particular by laser diffraction on a MALVERN type device (for example according to the NF ISO 13320 standard).

[0270] Additives

[0271] The crosslinkable two-component composition according to the invention may comprise at least one additive selected from the group consisting of catalysts, fillers (other than the thermally conductive filler), antioxidants, polymerization inhibitors, light stabilizers / UV absorbers, metal deactivators, antistatics, anti-hazing agents, foaming agents, biocides, plasticizers, lubricants, emulsifiers, colorants, pigments, rheological agents, toughness agents, impact modifiers, adhesion promoters, accelerators, optical brighteners, flame retardants, anti-seepage agents, nucleating agents, hardeners, solvents, and mixtures thereof.

[0272] These additives may be present in component A and / or component B of the composition according to the invention.

[0273] Examples of usable plasticizing agents include any plasticizing agent commonly used in the field of adhesives, such as epoxy resins, phthalates, benzoates, trimethylolpropane esters, trimethylolethane esters, trimethylolmethane esters, glycerol esters, pentaerythritol esters, naphthenic mineral oils, adipates, cyclohexyldicarboxylates, paraffinic oils, natural oils (possibly epoxidized), polypropylenes, polybutylenes, hydrogenated polyisoprenes, and mixtures thereof.

[0274] For example, one can use:

[0275] diisodecyl phthalate, such as that marketed for example under the name PALATINOL™ DIDP by BASF,

[0276] an ester of alkylsulfonic acid and phenol, such as, for example, marketed under the name MESAMOLL® by the company LANXESS,

[0277] diisononyl-1,2-cyclohexanedicarboxylate, such as that marketed, for example, under the name HEXAMOLL DINCH® by BASF,

[0278] pentaerythritol tetravalerate, such as marketed for example under the name PEVALEN™ by PERSTORP, epoxidized soybean oil such as marketed for example under the name VIKOFLEX® 7170 by ARKEMA.

[0279] The composition according to the invention may further comprise at least one organic and / or mineral filler (different from the thermally conductive filler).

[0280] The usable mineral filler is advantageously chosen so as to improve the mechanical performance of the composition according to the invention in the crosslinked state.

[0281] As an example of a usable mineral filler, any mineral filler commonly used in adhesive compositions can be employed. These fillers typically come in the form of particles with various geometries. They can be, for example, spherical, fibrous, or irregularly shaped.

[0282] Preferably, the filler is chosen from the group consisting of clay, quartz, carbonate fillers, kaolin, gypsum, clays, and mixtures thereof; preferably the filler is chosen from among carbonate fillers, such as alkali or alkaline-earth metal carbonates, and more preferably calcium carbonate or chalk.

[0283] These fillers can be untreated or treated, for example with an organic acid such as stearic acid, or a mixture of organic acids consisting mainly of stearic acid.

[0284] Hollow mineral microspheres can also be used, such as hollow glass microspheres, and more particularly those made of sodium and calcium borosilicate or aluminosilicate.

[0285] Adhesion promoters can be selected from acrylic acid, methacrylic acid, silanes, such as aminosilanes, epoxilanes or acryloyl silanes, or phosphate ester-based adhesion promoters such as, for example, 2-hydroxyethyl methacrylate phosphate ester, 2-methacryloyloxyethyl phosphate, bis-(2-methacryloyloxyethyl phosphate), 2-acryloyloxyethyl phosphate, bis-(2-acryloyloxyethyl phosphate), methyl-(2-methacryloyloxyethyl phosphate), ethyl-(2-methacryloyloxyethyl phosphate), a mixture of mono- and di-phosphate esters of 2-hydroxyethyl methacrylate.

[0286] When a pigment is present in the composition, its content is preferably less than or equal to 3% by weight, and preferably less than or equal to 2% by weight, relative to the total weight of the composition. When present, the pigment may, for example, represent from 0.1% to 3% by weight or from 0.4% to 2% by weight of the total weight of the composition. Pigments may be organic or inorganic.

[0287] For example, the pigment is TiO2, in particular KRONOS® 2059 marketed by the company KRONOS.

[0288] The composition may include 0.1% to 3%, preferably 1% to 3% by weight, of at least one UV stabilizer or antioxidant. These compounds are typically introduced to protect the composition from degradation resulting from a reaction with oxygen that may be formed by the action of heat or light. These compounds may include primary antioxidants that scavenge free radicals. Primary antioxidants may be used alone or in combination with other secondary antioxidants or UV stabilizers.

[0289] Examples include IRGANOX @ 1010, IRGANOX ® B561, IRGANOX ® 245, IRGAFOS ® 168, TINUVIN® 328 or TINUVIN™ 770 marketed by BASF.

[0290] The rheology agent can be any rheology agent commonly used in the field of adhesive compositions.

[0291] Preferably, the rheology agent is chosen from:

[0292] 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 book "Polyurethane Sealants", Robert M. Evans, ISBN 087762-998-6,

[0293] fumed silica, such as for example sold under the name HDK® N20 by WACKER;

[0294] urea derivatives resulting from the reaction of an aromatic diisocyanate monomer such as 4,4'-MDI with an aliphatic amine such as butylamine. The preparation of such urea derivatives is described in particular in application FR 1 591 172;

[0295] amide waxes such as, for example, CRAYVALLAC® SLT or CRAYVALLAC® SLA marketed by ARKEMA.

[0296] Preferably, the rheology agent does not include carboxylic acid functions.

[0297] Preferably, the rheology agent is chosen from among the amide waxes.

[0298] The term "amide waxes" refers to waxes comprising one or more compounds with at least one amide group. In particular, amide waxes can be obtained from fatty acid(s) (e.g., ricinoleic acid) and (di)amine(s).

[0299] 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.

[0300] The average particle size advantageously corresponds to the d50 particle size, i.e. the maximum size of 50% of the smallest particles by volume, and can be measured with a particle size analyzer, in particular by laser diffraction on a MALVERN type device (for example according to the NF ISO 13320 standard).

[0301] Unless otherwise stated, the standards mentioned throughout the application are those in effect on the date the application was filed.

[0302] The total content of rheology agent in component A can range from 0.4 to 0.6% by weight relative to the total weight of component A.

[0303] The total content of rheology agent in component B can range from 0.4 to 0.6% by weight relative to the total weight of component B.

[0304] The total content of rheology agent can range from 0.4% to 0.6%, preferably from 0.45% to 0.55% relative to the total weight of the composition.

[0305] The toughening agent may be chosen from solid and liquid elastomeric polymeric materials, such as, for example, olefinic-terminated elastomers (described in particular in US 4,223,115); olefinic urethane reaction products from an isocyanate functionalized prepolymer and an OH functionalized monomer (described in particular in US 4,223,115).

[0306] The toughening agent can also be an ABA triblock copolymer. For example, block A can be polystyrene, alpha-methylstyrene, t-butylstyrene, or other alkylated styrene rings, or mixtures thereof; while block B can be an elastomeric segment having a Tg of 0°C or less, such as, for example, a derivative of a conjugated diene, isobutylene, or other olefin. Commercial examples of block copolymers include the EUROPRENE® range marketed by Enichem Elastomers Americas, Inc.

[0307] Other high molecular weight toughness agents include, for example, sequenced copolymers and random copolymers including, but not limited to, polyethylene, polypropylene, styrene-butadiene, polychloroprene, EPDM, chlorinated rubber, butyl rubber, styrene / butadiene / acrylonitrile rubber and chlorosulfonated polyethylene.

[0308] Other toughness agents include, notably, liquid olefin terminated elastomers, where the elastomeric portion is based on butadiene homopolymers, butadiene copolymers, and at least one monomer copolymerizable therewith, for example, styrene, acrylonitrile, methacrylonitrile (e.g., poly(butadiene-(meth)acrylonitrile or poly(butadiene-(meth)acrylonitrile-styrene) and mixtures thereof); as well as modified elastomeric polymer materials, such as butadiene homopolymers and copolymers modified by copolymerization with these of traces of up to about 5 percent by weight of at least one functional monomer (such as acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, styrene and methyl methacrylate to give, for example, homopolymers and / or copolymers of polybutadiene terminated with methacrylate.

[0309] Polyalkadienes terminated by oiefins having carboxylic ester bonding groups and at least one nascent secondary hydroxyl group, as disclosed in US 5,587,433, may be included as toughening agents. The secondary OH group may optionally be capped using a diisocyanate as disclosed in US 5,641,834.

[0310] Specific examples of hydroxyl-terminated polybutadiene include the reaction of anhydride-modified OH-terminated PBD with an epoxy, such as glycidic substituents.

[0311] The content of toughening agent can range from 2% to 4% by weight, relative to the total weight of said composition.

[0312] Commercial examples of toughness agents include Hypro 1300X33 LC VTBNX marketed by Huntsman (CAS 118578-03-3) or Vamac DP marketed by Dupont, Epion EP 400v and 450 A marketed by Kaneka, and Europrene SOLT 614 marketed by Versalis.

[0313] In the composition according to the invention, the volume ratio of component A / component B can range from 20 / 1 to 1 / 1, preferably from 10 / 1 to 1 / 1. The volume ratio A / B is preferably 1 / 1.

[0314] The composition according to the invention preferably has, after crosslinking, a density at 23°C ranging from 1.7 to 1.9.

[0315] The density of the composition, after crosslinking, is preferably measured by mass measurement using a pycnometer, in particular according to the following method:

[0316] Introduce a known mass of the crosslinked product to be measured in density (M sample), fill with water up to the overflow of the pycnometer, note the mass -> deduce the volume of water (V1). Empty the pycnometer, dry it completely then reintroduce water again up to the overflow of the pycnometer, note the mass of water -> We can deduce the volume of water (V2).

[0317] The density of the crosslinked product is then obtained using the following formula:

[0318] (V2-V1) / MS = sample volume / MS = density in g / cm 3 The composition according to the invention preferably has, after crosslinking, a thermal conductivity greater than or equal to 1.5 W / (m / K), more preferably ranging from 1.5 to 2 W / (m. K).

[0319] The thermal conductivity of the composition, after crosslinking, is measured according to ASTM D5470-17.

[0320] Preferably, the composition, after crosslinking, has a density at 23°C / thermal conductivity ratio ranging from 0.85 to 1.25.

[0321] A preferred composition is a two-component, crosslinkable composition comprising: - a component A comprising:

[0322] • an oxidant chosen from copper salts of formula (III-1) or copper complex of formula (III-2), preferably the oxidant is copper(II) acetylacetonate;

[0323] • at least one (meth)acrylate monomer;

[0324] - a component B comprising:

[0325] • a reducing agent chosen from among the sulfinates of formula (XI), preferably from:

[0326]

[0327] said composition comprising at least one thermally conductive filler in component A and / or B;

[0328] said thermally conductive charge being chosen from among metallic oxides, metallic hydroxides, and their mixtures;

[0329] said composition having, after crosslinking, a density at 23°C ranging from 1.7 to 1.9; said composition having, after crosslinking, a density at 23°C / thermal conductivity ratio ranging from 0.85 to 1.25;

[0330] said composition being devoid of compounds comprising a peroxide group.

[0331] B. Ready-to-use kit

[0332] The present invention also relates to a ready-to-use kit comprising component A as defined above and component B as defined above, packaged in two separate compartments. This could, for example, be a two-component cartridge. Indeed, the composition according to the invention can be in two-component form, for example, within a ready-to-use kit comprising component A in a first compartment or drum and component B in a second compartment or drum, in proportions suitable for direct mixing of the two components, for example, using a dosing pump.

[0333] According to one embodiment of the invention, the kit further includes one or more means for mixing components A and B. Preferably, the mixing means are chosen from metering pumps, static mixers of diameter adapted to the quantities used.

[0334] C. Uses of the composition

[0335] The present invention also relates to the use of a crosslinkable two-component composition as defined above, as an adhesive, sealant or coating, preferably as an adhesive.

[0336] The present invention relates to the use of said composition for bonding (preferably structural or semi-structural) in electric vehicle batteries (such as, for example, car, bus, truck).

[0337] The present invention relates to a method for assembling two substrates by bonding, comprising:

[0338] the mixture of components A and B as defined above to form the composition as defined above;

[0339] coating at least one of the two substrates to be assembled with said composition; bringing the two substrates into actual contact; then

[0340] cross-linking of the composition.

[0341] The crosslinking step can be carried out at a temperature between 0°C and 200°C, preferably between 10°C and 150°C, preferably between 23 and 80°C and in particular between 20°C and 25°C.

[0342] Suitable substrates include, for example, inorganic substrates such as metals or alloys (such as aluminium alloys, steel, non-ferrous metals and galvanised metals); or organic substrates such as plastics such as PVC, polycarbonate, PMMA, polyethylene, polypropylene, polyesters, polyamides, epoxy resins; metal substrates and paint-coated composites.

[0343] Crosslinking can be achieved under electromagnetic irradiation, for example with a UV radiation source or an LED. Electromagnetic irradiation can be applied to the edges of the bond in the case of an opaque substrate, or directly through the substrate in the case of a transparent substrate.

[0344] The crosslinking step under electromagnetic irradiation can be carried out at a wavelength greater than 300 nm, preferably from 360 nm to 680 nm, and even more preferably from 360 nm to 420 nm.

[0345] The present invention relates to an electric vehicle battery comprising the crosslinked product comprising the composition according to the invention as described above.

[0346] All the embodiments described above can be combined with one another. In particular, the various aforementioned components of the composition, and especially the preferred embodiments, can be combined with one another.

[0347] In the context of the invention, "between x and y" or "ranging from x to y" means an interval in which the bounds x and y are included. For example, the range "between 0% and 25%" includes, in particular, the values ​​0% and 25%.

[0348] The invention is now described in the following embodiment examples which are given for illustrative purposes only, and should not be interpreted to limit its scope.

[0349] EXAMPLES

[0350] The following ingredients were used:

[0351] • Benzyl methacrylate: CAS 2495-37-6, marketed by Evonik as Visiomer BNMA

[0352] • HEMA: 2 Hydroxyethyl methacrylate CAS 868-77-9 marketed by the Röhm company as Meracryl HEMA 98

[0353] • Compound X: urethane methacrylate with a functionality of 2 and a number molecular weight of 2600 g / mol from Sartomer

[0354] • Methacrylic acid marketed by the company Sigma-Aldrich

[0355] • Cray Vallac SLT: micronized polyamide wax rheology additive marketed by Arkema

[0356] • Cu(acac)2: copper(II) acetylacetonate (CAS: 13395-16-9) available from SIGMA-ALDRICH

[0357] • SR 9054: mixture of mono- and diester of HEMA phosphate marketed by Sartomer (CAS: 52628-03-2)

[0358] • Lauryl methacrylate: (CAS 142-90-5) marketed by Sartomer as SR 313A • Hypro 1300X33 LC VTBNX: functionalized polybutadiene acrylonitrile methacrylate copolymer marketed by Huntsman (CAS 118578-03-3)

[0359] • Apyral HC 500: aluminum trihydroxide with a D50 = 30 microns, marketed by Nabaltec

[0360] • sodium p-toluenesulfinate (CAS: 824-79-3) available from SIGMA-ALDRICH

[0361] Example 1: Preparation of the composition

[0362] In a mixer maintained under constant agitation and under air, the ingredients of component A are mixed in the proportions indicated in the following table at a temperature of 23°C.

[0363] In a mixer maintained under constant agitation and under air, the different ingredients constituting component B are mixed in the proportions indicated in the following table at a temperature of 23°C.

[0364] Component A and component B are mixed in a 1:1 volume ratio using a Sulzer® mixpac mixer at an ambient temperature of 23°C. The following composition was prepared:

[0365]

[0366]

[0367] Example 2: Composition performance

[0368] Measuring responsiveness:

[0369] Reactivity monitoring is performed using a thermocouple probe.

[0370] The two-component cartridge is first purged, then components A and B are mixed using a static mixer. After purging the mixture, 30 g of adhesive is placed in a perforated container, and a temperature probe is inserted to monitor the exothermic reaction.

[0371] The peak time is the time required to reach the peak temperature (maximum of the exotherm observed during polymerization).

[0372] Bonding tests (ISO 4587) according to the protocol below

[0373] The bonds are made on aluminum sterigmas from Rocholl. On one sterigma, a 25 x 12.5 mm area was marked out using 250 µm thick Teflon spacers. This area was filled with the composition to be tested, then a second sterigma of the same material was bonded to it. The bonds were then placed in a climate-controlled room at 23°C and 50% humidity for 24 hours to allow complete curing of the adhesive before testing.

[0374] The purpose of tensile testing on a dynamometer is to evaluate the maximum force (in MPa) that must be applied to the joint to separate it. A tensile testing machine allows a simple lap joint placed between two rigid supports to be subjected to shear stress until failure by applying tension to the supports parallel to the joint surface and the main axis of the specimen. The result to be recorded is the maximum force observed during the test. The shear stress is applied via the moving jaw of the tensile testing machine at a speed of 5 mm / min. This tensile testing method is performed as defined by ISO 4587. At the end of the mechanical characterization, the failure mode of the bond is evaluated. This mode can be cohesive, adhesive, or a hybrid of cohesive and adhesive, in which case it is called semi-cohesive.

[0375] Mechanical tensile test method (ISO 37, specimen H2) according to the protocol below:

[0376] The intimate mixture of the two parts of the two-component adhesive is poured into Teflon molds sculpted with the imprint of the H2 specimen to be produced.

[0377] A PET film is used to cover the surface of the Teflon mold filled with adhesive in order to limit inhibition by oxygen and the Teflon mold is left for 24 hours at 23°C to allow complete crosslinking of the adhesive.

[0378] The H2 test specimens are then demolded and deburred in preparation for tensile tests carried out using a dynamometer equipped with an extensometer to better appreciate their elongation at break.

[0379] The tests are carried out in a laboratory with controlled humidity and temperature (50°H ±5 and 23°C ± 2°C)

[0380] The tensile tests are conducted according to ISO Standard 37 with the following test characteristics: Sensor: 2.5 KN / Preload: 1 / Test speed: 100 mm / min.

[0381] From the tensile curves obtained, we typically note:

[0382] The maximum stress in MPa is the maximum value of the tensile curve.

[0383] The breaking strength in MPa

[0384] Young's modulus in MPa, representing the slope at the origin of the tensile curve. Elongation at break in %

[0385] Test method for measuring thermal conductivity according to ASTM D5470-17: Component A and component B are mixed in a 1:1 volume ratio using a Sulzer® mixpac mixer at an ambient temperature of 23°C. Crosslinking was carried out at 23°C and 50% relative humidity for 24 hours.

[0386] A 10 cm diameter, 2 mm thick disc of the sample to be analyzed is prepared, from which three 30 mm diameter discs will be taken for analysis. In the analysis according to the steady-state cylinder method of ASTM D5470-17, the sample disc whose thermal conductivity is to be measured is placed between two cylinders of a reference material with known thermal conductivity. To ensure conductivity, the surface of the sample discs is coated with a contact agent (thermal grease).

[0387] Thermal conductivity is given by measuring the heat flux recovered from a perfectly known incoming heat flux through the assembly described above.

[0388] Test method for measuring density using a pycnometer

[0389] Component A and component B were mixed in a 1:1 volume ratio using a Sulzer® mixpac mixer at an ambient temperature of 23°C. Crosslinking was carried out at 23°C and 50% relative humidity for 24 hours.

[0390] Introduce a known mass of the crosslinked product to be measured in density (M sample), fill with water up to the overflow of the pycnometer, note the mass -> deduce the volume of water (V1). Empty the pycnometer, dry it completely then reintroduce water again up to the overflow of the pycnometer, note the mass of water -> We can deduce the volume of water (V2).

[0391] The density of the crosslinked product is then obtained using the following formula:

[0392] (V2-V1) / MS = sample volume / MS = density in g / cm 3

[0393] The results obtained are given in the table below:

[0394]

Claims

1. CLAIMS 1. Two-component, crosslinkable composition comprising:

3. A component A comprising: 4.• an oxidant; 5.• at least one (meth)acrylate monomer; 6. A component B comprising: 7.• a reducer; 8. Said composition comprising at least one thermally conductive charge in component A and / or B; 9. said composition having, after crosslinking, a density at 23°C ranging from 1.6 to 2.2; said composition having, after crosslinking, a density at 23°C / thermal conductivity ratio ranging from 0.80 to 1.30; 10. Said composition being devoid of compounds comprising a peroxide group.

2. Composition according to claim 1, wherein the oxidant is selected from the group consisting of: organic copper derivatives, iodoniums, thiopheniums, sulfoniums, thianthreniums, their derivatives, and mixtures thereof.

3. Composition according to any one of claims 1 or 2, wherein the oxidant is selected from the group consisting of:

13. Compounds of the following formulas (la) or (Ib):

15. 17.(la (Ib) 18. in which:

19. each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R a , and R b represents, independently of each other, a radical chosen from the group consisting of a hydrogen atom, a halogen, an alkyl, a cycloalkyl or an aryl; 20.R f represents a perhaloalkyl or haloalkyl; X' represents an anion; 21.- of the following compounds with formula (Ha) or (llb) or (Ile):

25.

27. in which: 28.R 9 and R 10each represent, independently of each other, a hydrogen atom, an alkyl radical, an alkenyl radical, a cycloalkyl radical, a cycloalkenyl radical, an aryl radical, a chlorine atom, a bromine atom, an iodine atom, a carboxylic radical, or a -NO2 radical; 29.Z' represents a monovalent anion; 30.- W represents O or S; 31.- copper salts of formula (111-1) or a copper complex of formula (III-2):

33.

34. in which: - R and R” each represent, independently of each other, an alkyl radical, a cycloalkyl radical, an aryl radical, a heteroaryl radical, said alkyl, cycloalkyl, aryl, heteroaryl radicals being optionally substituted by one or more halogen atoms such as, for example, by one or more fluorine atoms; 35.- R' represents a hydrogen atom, an alkyl radical, a cycloalkyl radical, an aryl radical, a heteroaryl radical, 36.or R and R' (or R' and R") can also be engaged in a single ring comprising from 5 to 8 carbon atoms, said ring possibly comprising at least one heteroatom (such as for example O, S); 37.- R'” represents an alkyl radical, a cycloalkyl radical, an aryl radical, a heteroaryl radical, said alkyl, cycloalkyl, aryl, heteroaryl radicals possibly being substituted by one or more halogen atoms such as for example by one or more fluorine atoms; 38.- and their mixtures.

4. Composition according to any one of claims 1 to 3, wherein the (meth)acrylate monomer is selected from:

40. Mono-(meth)acrylates preferably selected from the group consisting of methyl methacrylate; ethyl (meth)acrylate; n-propyl (meth)acrylate; n-butyl (meth)acrylate; isobutyl (meth)acrylate; sec-butyl (meth)acrylate; tert-butyl (meth)acrylate; n-hexyl (meth)acrylate; 2-ethylhexyl (meth)acrylate; n-octyl (meth)acrylate; isooctyl (meth)acrylate; n-decyl (meth)acrylate; n-dodecyl (meth)acrylate; tridecyl (meth)acrylate; tetradecyl (meth)acrylate; hexadecyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate; 2- and 3-hydroxypropyl (meth)acrylate; 2-methoxyethyl (meth)acrylate; 2-ethoxyethyl (meth)acrylate; 2- and 3-ethoxypropyl (meth)acrylate; tetrahydrofurfuryl (meth)acrylate; alkoxylated tetrahydrofurfuryl (meth)acrylate; 2-(2-ethoxyethoxy)ethyl (meth)acrylate; cyclohexyl (meth)acrylate; glycidyl (meth)acrylate; isodecyl (meth)acrylate;lauryl (meth)acrylate; 2-phenoxyethyl (meth)acrylate; alkoxylated phenol (meth)acrylates; alkoxylated nonylphenol (meth)acrylates; cyclic trimethylolpropane (meth)acrylate formal; glycerol (meth)acrylate carbonate; glycerol (meth)acrylate formal; hydroxyethyl (meth)acrylate; isobornyl (meth)acrylate; tricyclodecanemethanol (meth)acrylate; tert-butylcyclohexanol (meth)acrylate; trimethylcyclohexanol (meth)acrylate; diethylene glycol monomethyl ether (meth)acrylate; benzyl (meth)acrylate; diethylene glycol monoethyl ether (meth)acrylate; diethylene glycol monobutyl ether (meth)acrylate; triethylene glycol monoethyl ether (meth)acrylate; ethoxylated lauryl (meth)acrylate; (Meth)acrylates of methoxy polyethylene glycol; (Meth)acrylates of 3-(2-hydroxyalkyl)oxazolidinone; and mixtures thereof; 41. - (Meth)acrylate monomers containing two or more (meth)acrylate groups per molecule, preferably selected from bisphenol A di(meth)acrylate; hydrogenated bisphenol A di(meth)acrylate; ethylene glycol di(meth)acrylate; diethylene glycol di(meth)acrylate; triethylene glycol di(meth)acrylate; tetraethylene glycol di(meth)acrylate; polyethylene glycol di(meth)acrylate; propylene glycol di(meth)acrylate; dipropylene glycol di(meth)acrylate; tripropylene glycol di(meth)acrylate; tetrapropylene glycol di(meth)acrylate; polypropylene glycol di(meth)acrylate; polytetramethylene glycol di(meth)acrylate; 1,2-butanediol di(meth)acrylate; 2,3-butanediol di(meth)acrylate; 1,3-butanediol di(meth)acrylate; 1,4-butanediol di(meth)acrylate; 1,5-pentanediol di(meth)acrylate; 1,6-hexanediol di(meth)acrylate; 1,8-octanediol di(meth)acrylate; 1,9-nonanediol di(meth)acrylate; 1,10-nonanediol di(meth)acrylate;1,12-dodecanediol di(meth)acrylate; neopentyl glycol di(meth)acrylate; 2-methyl-2,4-pentanediol di(meth)acrylate; polybutadiene di(meth)acrylate; cyclohexane-1,4-dimethanol di(meth)acrylate; tricyclodecane and dimethanol di(meth)acrylate; metallic di(meth)acrylates; modified metallic di(meth)acrylates; glyceryl di(meth)acrylate; glyceryl tri(meth)acrylate; trimethylolethane tri(meth)acrylate; trimethylolethane di(meth)acrylate; trimethylolpropane tri(meth)acrylate; trimethylolpropane di(meth)acrylate; pentaerythritol di(meth)acrylate; pentaerythritol tri(meth)acrylate; pentaerythritol tetra(meth)acrylate; di(trimethylolpropane) diacrylate; di(trimethylolpropane) triacrylate; di(trimethylolpropane) tetraacrylate, sorbitol penta(meth)acrylate; di(pentaerythritol)tetraacrylate; di(pentaerythritol) pentaacrylate; di(pentaerythritol)hexa(meth)acrylate;tri(meth)acrylate of tris (2-hydroxyethyl) isocyanurate; as well as their alkoxylated derivatives (e.g. ethoxylated and / or propoxylated); and mixtures thereof; 42.- and their mixtures.

5. Composition according to any one of claims 1 to 4, wherein the (meth)acrylate monomer of component A is selected from lauryl (meth)acrylate, hydroxyethyl methacrylate, and their mixtures.

6. Composition according to any one of claims 1 to 5, characterized in that it further comprises at least one (meth)acrylate oligomer or one (meth)acrylate polymer.

7. Composition according to any one of claims 1 to 6, characterized in that it comprises from 2% to 10%, preferably from 5% to 10% by weight of (meth)acrylate oligomers and / or (meth)acrylate polymers relative to the total weight of said composition.

8. Composition according to any one of claims 1 to 7, wherein the reducing agent is selected from the group consisting of polyamines, dihydropyridine compounds, sulfinates, aromatic phosphines, and mixtures thereof.

9. Composition according to any one of claims 1 to 8, wherein the reducing agent is selected from the sulfinates of the following formula (XI): 47.[R a -SO2-] P Q P+ (XI) 48. in which: 49.- R a represents an aryl or heteroaryl radical, said heteroaryl and aryl being possibly substituted by at least one of the following radicals: F, OH, C(O)OMe, NHC(O)Me, methyl (Me), CF3, OH or SO2-; 50.- Q represents Li, Na, K or Zn, preferably Na or K; 51.- p represents 1 or 2; 52. Preferably, the reducing agent is chosen from the following compounds:

53.

10. Composition according to any one of claims 1 to 9, wherein:

56. The oxidant for component A is chosen from copper salts of formula (III-1) or copper complexes of formula (III-2); preferably the oxidant is copper(II) acetylacetonate; and 57. The reducing agent for component B is chosen from among the sulfinates of formula (XI), preferably from:

60.

11. Composition according to any one of claims 1 to 10, wherein the thermally conductive charge has a thermal conductivity greater than or equal to 5 W / mK, preferably greater than or equal to 10 W / mK, more preferably greater than or equal to 20 W / mK.

12. Composition according to any one of claims 1 to 11, wherein the thermally conductive filler is selected from aluminosilicates, aluminum nitride, boron nitride, metal oxides (such as, for example, zinc oxide, magnesium oxide, beryllium oxide, titanium oxide, nickel oxide, copper oxide, tin oxide or aluminum oxide), metal hydroxides (such as, for example, aluminum hydroxide (also called ATH or aluminum trihydroxide, of formula Al(OH)3), cadmium hydroxide (Cd(OH)2), lead(II) hydroxide (Pb(OH)2), zinc hydroxide (Zn(OH)2), 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), iron hydroxides), metals (such as copper), carbon black, and mixtures thereof.

13. Composition according to any one of claims 1 to 12, wherein the thermally conductive filler is selected from metal oxides, metal hydroxides, and mixtures thereof.

14. Composition according to any one of claims 1 to 13, characterized in that each of the components A and B comprises at least one thermally conductive filler.

15. Composition according to any one of claims 1 to 14, characterized in that the total content of thermally conductive filler(s) in the total composition ranges from 50% to 95% by weight, preferably from 60% to 90% by weight, and even more preferably from 65% to 85% by weight, relative to the total weight of the composition.

16. Composition according to any one of claims 1 to 15, characterized in that it comprises at least 60% by weight of aluminium hydroxide relative to the total weight of all thermally conductive fillers, preferably at least 80% by weight, and even more preferably the composition comprises 100% aluminium hydroxide as thermally conductive fillers.

17. Composition according to any one of claims 1 to 16, characterized in that it has, after crosslinking, a density at 23°C ranging from 1.7 to 1.

9.

18. Composition according to any one of claims 1 to 17, characterized in that, after crosslinking, it has a thermal conductivity greater than or equal to 1.5 W / (m / K), more preferably ranging from 1.5 to 2 W / (m. K).

19. Composition according to any one of claims 1 to 18, characterized in that, after crosslinking, it has a density at 23°C / thermal conductivity ratio of 0.85 to 1.

25.

20. Use of the composition according to any one of claims 1 to 19, for bonding (preferably structural or semi-structural) in electric vehicle batteries (such as for example car, bus, truck).

21. Electric vehicle battery comprising the crosslinked product comprising the composition according to any one of claims 1 to 19.

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