Composition based on (meth)acrylate compounds

Abstract

Composition based on (meth)acrylate compounds. The present invention relates to a two-component crosslinkable composition comprising: - a component A comprising: an organic copper derivative; at least one (meth)acrylate compound M1; provided that when the organic copper derivative is not halogenated, then component A further comprises a halogenated carboxylic acid; - a component B comprising at least one compound having the following formula (VI): [Ra-SO2-]p, Qp+ (VI) and their uses. Figure: None

Description

Title of the invention: Composition based on (meth)acrylate compounds. FIELD OF THE INVENTION

[0001] The present invention relates to a composition based on (meth)acrylate compound.

[0002] The invention also relates to the use of said composition for the semi-structural or structural repair and / or bonding of materials, for example in the fields of transport, marine, assembly, electronics, or construction. TECHNOLOGICAL BACKGROUND

[0003] Acrylic compositions are known reactive systems that crosslink by radical polymerization. They are used as adhesives, sealants, and coatings. Radical polymerization is typically initiated by a redox system which, through a redox reaction, leads to the production of radicals.

[0004] The majority of acrylic systems are two-component systems. The first component traditionally contains the reducing agent and the 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.

[0005] Most current acrylic systems use peroxide / amine couples to initiate the redox reaction. However, these systems suffer from several drawbacks such as stability problems, low reactivity with, in particular, long open times, and a lack of versatility...

[0006] There is a need for new compositions that make it possible to remedy at least partially one or more of these drawbacks.

[0007] In particular, there is a need for new compositions with high reactivity (high cohesion buildup), regardless of the associated open time. A. Composition

[0008] The present invention relates to a two-component crosslinkable composition comprising:

[0009] - a component A comprising: • an organic copper derivative; • at least one (meth)acrylate compound Ml;

[0010] provided that when the organic copper derivative of component A is not halogenated then component A further comprises a halogenated carboxylic acid;

[0011] - a component B comprising at least one compound having the following formula (VI): [r^o^qt (VI)

[0012] in which:

[0013] - Ra 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), CF3OH or SO2;

[0014] - Q represents Li, Na, K or Zn, preferably Na or K;

[0015] - p represents 1 or 2.

[0016] 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.

[0017] In the context of the invention, "C4 to C20 alkyl" means a linear or branched alkyl comprising 4 to 20 carbon atoms.

[0018] In the context of the 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.

[0019] In the context of the 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.

[0020] In the context of the invention, "aryl" means a monocyclic or bicyclic aromatic radical preferably comprising 6 to 12 carbon atoms. Phenyl is an example.

[0021] In the context of the 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.

[0022] 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.

[0023] In the context of the 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.

[0024] In the context of the invention, "cycloalkyl" means a saturated monocyclic or polycyclic system, preferably monocyclic or bicyclic, preferably comprising from 3 to 12 carbon atoms, the rings being able to be in pairs fused or bridged, such as the cyclopropyl, cyclopentyl, cyclohexyl or norbomyl groups.

[0025] 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.

[0026] In the context of the invention, "cycloalkenyl" means a monocyclic or polycyclic system, comprising at least one double bond, preferably comprising from 3 to 12 carbon atoms, the rings being able to be fused or bridged in pairs.

[0027] In the context of the invention, "alkoxy" means an -O-alkyl radical. Component A Organic copper derivative

[0028] The composition according to the invention comprises an organic copper derivative, preferably an organic copper(II) derivative.

[0029] The organic copper derivative may be halogenated or non-halogenated.

[0030] The organic copper derivative can be chosen from the group consisting of a salt of copper of formula (VIL1) or a copper complex of formula (VIL2):

[0031] in which:

[0032] - 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;

[0033] - R' represents a hydrogen atom, an alkyl radical, a cycloalkyl radical, a aryl radical, a heteroaryl radical,

[0034] 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);

[0035] - R'” represents 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.

[0036] Among the copper salts of formula (VII-1), examples may be given to copper(II) acetate (for example anhydrous or monohydrate), copper(II) monofluoroacetate, copper(II) difluoroacetate, copper(II) trifluoroacetate (for example anhydrous or monohydrate), copper(II) hexanoate, copper(II) ethyl-2-hexanoate, and mixtures thereof.

[0037] According to a preferred embodiment, in formula (VII-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.

[0038] Among the copper complexes of formula (VII-2), examples 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), having respectively the following formulas:

[0039] According to a preferred embodiment, in formula (VII-2):

[0040] - R represents an alkyl radical, a cycloalkyl radical, an aryl radical, a radical heteroaryl, preferably an alkyl radical;

[0041] - R' represents a hydrogen;

[0042] - R' ' represents an alkyl radical possibly substituted by one or more halogen atoms, such as for example one or more fluorine atoms.

[0043] The organic copper derivative is preferably a copper complex of formula (VIL2) and more particularly copper(II) acetylacetonate (Cu(acac)2).

[0044] The total content of organic copper derivative(s), and in particular of formula (VIL1) or (VIL2) can range from 0.05% to 5% by weight, preferably from 0.1% to 2% by weight, and even more preferably from 0.2% to 1% by weight relative to the total weight of the crosslinkable two-component composition. Halogenated carboxylic acid

[0045] According to the invention, when the organic copper derivative of component A as defined above is not halogenated then component A further comprises a halogenated carboxylic acid.

[0046] Note that when the organic copper derivative is halogenated, then component A may optionally include a halogenated carboxylic acid.

[0047] The halogenated carboxylic acid can be chosen from monohalogenated (comprising one halogen atom), dihalogenated (comprising two halogen atoms) or trihalogenated (comprising three halogen atoms) carboxylic acids.

[0048] 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.

[0049] Preferably, the halogenated carboxylic acid is chosen from dichloroacetic acid, difluoroacetic acid and mixtures thereof.

[0050] When present, the total content of halogenated carboxylic acid(s) can range from 0.5% to 20% by weight, preferably from 0.5% to 10% by weight, and even more preferably from 0.5% to 2% by weight relative to the total weight of the crosslinkable two-component composition. (Meth)acrylate compound ml

[0051] Component A comprises at least one (meth)acrylate compound ML

[0052] The (meth)acrylate compound Ml can be a (meth)acrylate monomer, an (meth)acrylate oligomer, or a (meth)acrylate polymer.

[0053] Preferably, the (meth)acrylate compound Ml is a (meth)acrylate monomer.

[0054] The (meth)acrylate compound Ml may have the following formula (F):

[0055] in which:

[0056] - R1 represents H or methyl;

[0057] - G represents an organic radical.

[0058] Preferably, G is chosen from the group consisting of alkyls, cycloalkyls, alkenyls, cycloalkenyls, alkylaryls, arylalkyls or aryls, said alkyls, cycloalkyls, alkenyls, cycloalkenyls, alkylaryls, arylalkyls and aryls being optionally substituted, for example, substituted by an alkyl or a hydroxyl.

[0059] The (meth)acrylate compound Ml may have one of the following formulas (I), (II), (III), (IV) or (V): □ (I) (V)

[0060] in which:

[0061] - R1 represents H or methyl;

[0062] - R2 represents H, methyl or ethyl;

[0063] - p represents 0 or 1; and

[0064] - Z represents H, O, S, an alkyl group, a benzyl group, an aryl group, or a alkoxy group;

[0065] - Y represents O, S, NH or CH2;

[0066] - a single bond or a double bond,

[0067] provided that when Z represents O, then the bond ^^> is a double bond; - G' is chosen from the group consisting of alkyls, cycloalkyls, alkenyls, cycloalkenyls, alkylaryls, arylalkyls or aryls, said alkyls, cycloalkyls, alkenyls, cycloalkenyls, alkylaryls, arylalkyls and aryls being possibly substituted by an alkyl group, said group G' being characterized in that it does not comprise a heteroatom; - G' ' is an alkyl substituted by an OH group.

[0068] In the aforementioned formula (I), G' can be selected from the group consisting of C1-C20 alkyls, preferably C4-C20 alkyls, cycloalkyls, alkenyls, cycloalkenyls, alkylaryls, arylalkyls or aryls, said alkyls, cycloalkyls, alkenyls, cycloalkenyls, alkylaryls, arylalkyls and aryls being optionally substituted by an alkyl group, said group G' being characterized in that it does not comprise a heteroatom.

[0069] In the aforementioned formula (I), G' is preferably chosen from the group consisting of alkyls (preferably C1-C20, and even more preferably C4-C20), cycloalkyls, or aryls, said alkyls, cycloalkyls, and aryls optionally being substituted by an alkyl group, said group G' being characterized in that it does not comprise a heteroatom. Preferably, G' is chosen from among the cycloalkyls.

[0070] Among the cycloalkyls, examples include isobomyl, tert-butyl cyclohexyl, trimethylcyclohexyl, dicyclopentenyl, tricyclodecyl.

[0071] Among the compounds of formula (I), examples include methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-butyl (meth)acrylate, heptyl (meth)acrylate, 2-tert-butylheptyl (meth)acrylate, octyl (meth)acrylate, 3-isopropylheptyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, 5-methylundecyl (meth)acrylate, dodecyl (meth)acrylate, 2-methyldodecyl (meth)acrylate, tridecyl (meth)acrylate, 5-methyltridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, 2-methylhexadecyl (meth)acrylate, heptadecyl (meth)acrylate, 5-isopropylheptadecyl (meth)acrylate, 4-tert-butyloctadecyl (meth)acrylate, 5-ethyloctadecyl (meth)acrylate, 3-isopropyloctadecyl (meth)acrylate, octadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, bornyl (meth)crylate, 2,3,4,5-tetra-t-butylcyclohexyl (meth)acrylate; benzyl (meth)acrylate, phenyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, isobomyl (meth)acrylate, and mixtures thereof.

[0072] The preferred Ml compounds of formula (I) are as follows:

[0073] Among the compounds Ml of formula (II) mentioned above, the following monomers may be cited for example:

[0074] (II-A) (II-B) (II-C)

[0075] Among the compounds Ml of formula (III) mentioned above, the following monomers may be cited for example:

[0076] (III-A) (mB)

[0077] (III-C) (III-D)

[0078] (III-E) (lïï-F)

[0079] Among the compounds Ml of formulas (II) or (III), the following monomers and their mixtures are preferred:

[0080] (III-F) (II-A)

[0081] (III-A)

[0082] Among the compounds Ml of formula (V), we can cite for example hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate.

[0083] The total content of compound(s) (meth)acrylate Ml in component A may be greater than or equal to 5% by weight, preferably greater than or equal to 20% by weight, even more preferably greater than or equal to 50% by weight, and even more advantageously greater than or equal to 70% by weight relative to the total weight of said component A.

[0084] The content of (meth)acrylate compound(s) Ml in the crosslinkable two-component composition according to the invention can range from 5% to 99% by weight, preferably from 20% to 99%, even more preferably from 50% to 99% by weight, and even more advantageously from 75% to 99% by weight relative to the total weight of said crosslinkable two-component composition.

[0085] The monomer (meth)acrylate Ml can be a recycled or non-recycled monomer. PI photoinitiator (optional)

[0086] Component A may further include a photoinitiator PL

[0087] The photoinitiator can be any photoinitiator known to those skilled in the art. Under the action of UV-visible radiation, the photoinitiator typically generates radicals that are responsible for initiating the photopolymerization reaction, and in particular increases the efficiency of the photopolymerization reaction. 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 from 300 to 420 nm. Advantageously, the UV or visible radiation source can be an LED.

[0088] The photoinitiator PI can be selected from the group consisting of:

[0089] - type I photoinitiators selected from:

[0090] - the family of acetophenones and alkoxyacetophenones, such as for example the 2,2-dimethoxy-2-phenylacetophenone and 2-diethyl-2-phenylacetophenone;

[0091] - 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;

[0092] - 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;

[0093] - the family of benzoin ethers, such as, for example, benzyl, methyl ether of benzoin and isopropyl benzoin ether;

[0094] - the family of phosphine oxides, such as, for example, oxide of diphenyl-(2,4,6-trimethylbenzoyl)phosphine (TPO), ethyl-(2,4,6-trimethylbenzoyl)phenylphosphine oxide (TPO-L) and bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylphenyl phosphine oxide (BAPO);

[0095] - the family of metallocenes, such as for example ferrocene, bis(eta 5-2,4- titanium cyclopentadiene-l-yl)-bis(2,6-difluoro)-3-(lH-pyrrole-l-yl)-phenyl) and iron (cumene)cyclopentadienyl hexafluorophosphate;

[0096] - Type II photoinitiators selected from:

[0097] - the benzophenone family, such as, for example, 4-phenylbenzophenone, the 4-(4'-methylphenylthio)benzophenone, the l-[4[ (4-benzoylphenyl)thio]phenyl]-2-methyl-2-[(4-methylphenyl)sulfonyl]-1-propanone;

[0098] - the thioxanthone family, such as, for example, isopropylthioxanthone (ITX), the 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2-chlorothioxanthone and 1-chloro-4-isopropylthioxanthone;

[0099] - the family of formate benzoyl esters, such as for example the methylbenzoylformate;

[0100] - the dibenzylidene ketone family, such as for example p- dimethylaminoketone;

[0101] - the coumarin family, such as for example 5-methoxy coumarin and 7- methoxy, 7-diethylamino coumarin and N-phenyleglycine coumarin;

[0102] - photoinitiators from the dye family such as, for example, triazines, fluorones, cyanines, safranines, 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;

[0103] - and mixtures thereof.

[0104] According to a preferred embodiment, the photoinitiator PI is selected from:

[0105] - the family of phosphine oxides, such as, for example, oxide of diphenyl-(2,4,6-trimethylbenzoyl)phosphine (TPO), ethyl-(2,4,6-trimethylbenzoyl)phenylphosphine oxide (TPO-L) and bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylphenyl phosphine oxide (BAPO);

[0106] - the thioxanthone family, such as for example isopropylthioxanthone (ITX), the 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2-chlorothioxanthone and 1-chloro-4-isopropylthioxanthone;

[0107] the photoinitiator PI being even more preferentially chosen from diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), and ethyl-(2,4,6-trimethylbenzoyl)phenylphosphine oxide (TPO-L).

[0108] The total PI photoinitiator content can 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.

[0109] 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. Component B Compound of formula (VI)

[0110] Component B comprises at least one compound having the following formula (VI): [YES] [Ra-SO2]p, Qp+(VI)

[0112] in which:

[0113] - Ra 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;

[0114] - Q represents Li, Na, K or Zn, preferably Na or K;

[0115] - p represents 1 or 2.

[0116] The compound of formula (VI) may be selected from the following compounds: N / A

[0117] According to a preferred embodiment, the compound of formula (VI) is chosen from the following compounds:

[0118] The total content of compound(s) of formula (VI) as defined above can range from 0.1% to 5.0% by weight, preferably from 0.1% to 3.0% by weight, and even more preferably from 0.2% to 1.5% by weight relative to the total weight of the crosslinkable two-component composition according to the invention. (meth)acrylate compounds

[0119] Component B may comprise one or more (meth)acrylate Ml compound(s) as defined for component A.

[0120] Preferably, component B comprises the same (meth)acrylate compound Ml as in component A.

[0121] Component B may comprise more than 5% by weight of compound(s) Ml, preferably more than 20% by weight, and advantageously more than 50% by weight of compound(s) Ml, preferably even more than 70% by weight, and even more preferably more than 90% by weight, relative to the total weight of said component B.

[0122] Component B may include, in particular, from 60% to 99.9% by weight of compound(s) Ml, and preferably from 80% to 99.5% by weight, relative to the total weight of said component B.

[0123] Preferably, the (meth)crylate Ml compound of component B does not comprise any acid groups. The acid groups may be a phosphoric acid group, a thiophosphoric acid group, a phosphonic acid group, a sulfonic acid group, and a carboxylic acid group. For example, the (meth)acrylate Ml compound in component B is not 10-methacryloyloxydecyldihydrogen phosphate. Composition

[0124] The crosslinkable two-component composition according to the invention may comprise at least one additive selected from the group consisting of catalysts, fillers, antioxidants, polymerization inhibitors, light stabilizers / UV absorbers, metal deactivators, antistatic agents, anti-hazing agents, foaming agents, biocides, plasticizers, lubricants, emulsifiers, dyes, pigments, rheological agents, impact modifiers, adhesion promoters, accelerators, optical brighteners, flame retardants, anti-seepage agents, nucleating agents, solvents, and mixtures thereof.

[0125] These additives may be present in component A and / or component B of the composition according to the invention.

[0126] By way of example of a usable plasticizing agent, any plasticizing agent commonly used in the field of adhesives may be cited, such as, for example, 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.

[0127] For example, one can use: - diisodecyl phthalate, such as that marketed, for example, under the name PALATINOL™ DIDP by BASF, - an ester of alkylsulfonic acid and phenol, such as, for example, marketed under the name MESAMOLL® by LANXESS, - diisononyl-1,2-cyclohexanedicarboxylate, such as, for example, marketed under the name HEXAMOLL DINCH® by BASF, - pentaerythritol tetravalerate, such as, for example, marketed under the name PEVALEN™ by PERSTORP, - Epoxidized soybean oil such as, for example, marketed under the name VIKOFLEX® 7170 by the ARKEMA Company.

[0128] As an example of usable (thixotropic) rheology agent(s), any rheology agent commonly used in the field of adhesive compositions may be cited.

[0129] Preferably, the thixotropic agents are chosen from: - PVC plastisols, corresponding to a suspension of PVC in a plasticizing agent miscible with PVC, obtained in situ by heating to temperatures ranging from 60°C to 80°C. These plastisols may be those described in particular in the book "Polyurethane Sealants", Robert M. Evans, ISBN 087762-998-6, - fumed silica, such as for example sold under the name HDK® N20 by WACKER; - urea derivatives resulting from the reaction of an aromatic diisocyanate monomer such as 4,4'-MDI with an aliphatic amine such as butylamine. The preparation of such urea derivatives is described in particular in application FR 1 591 172; - micronized amide waxes, such as CRAYVALLAC® SLT or CRAYVALLAC® SLA marketed by ARKEMA.

[0130] The composition according to the invention may further comprise at least one organic and / or mineral filler.

[0131] 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.

[0132] As an example of a usable mineral filler, any mineral filler commonly used in the field of adhesive compositions may be used. These fillers typically take the form of particles of various geometries. They may, for example, be spherical, fibrous, or have an irregular shape.

[0133] 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.

[0134] 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.

[0135] Hollow mineral microspheres such as hollow glass microspheres, and more particularly those made of sodium and calcium borosilicate or aluminosilicate, can also be used.

[0136] The charge can be an electrically and / or thermally conductive charge.

[0137] Among electrically conductive charges, examples may be given to carbon black, graphite, carbon fibers, a metal M' possibly coated by a layer of metal M”, a mineral or organic charge coated by a layer of metal, and mixtures thereof.

[0138] Among the metals coated by a layer of metal, we can cite for example copper coated with a layer of silver.

[0139] Organic fillers can be coated with a layer of metal such as silver or copper. For example, polymethyl methacrylate (PMMA) coated with a layer of silver.

[0140] Examples of thermally conductive fillers include carbon black powders, graphite, carbon fibers (CFTs), metal oxides, metal hydroxides, metal silicates, metal sulfides, boron nitride, and aluminum nitride. The metals in the metallic compounds are by Examples chosen from tin, indium, antimony, aluminum, titanium, iron, magnesium, zinc, ... Electrically and / or thermally conductive charges can be found in the form of spherical particles, tubes, flakes or fibers having in particular a specific surface area ranging from 0.01 m2 / g to 100 m2 / g.

[0141] Preferably, the composition comprises electrically conductive charges.

[0142] The composition according to the invention may comprise from 0% to 95% by weight, preferably from 40% to 95% by weight of one or more electrically and / or thermally conductive charge(s) relative to the total weight of said composition.

[0143] Preferably, the electrically and / or thermally conductive charges are in component B of said composition.

[0144] The composition according to the invention may further comprise at least one adhesion promoter, preferably selected from 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.

[0145] When a pigment is present in the composition, its content is preferably less than or equal to 3% by weight, and more 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.

[0146] The pigments can be organic or inorganic pigments.

[0147] For example, the pigment is TiO2, in particular KRONOS® 2059 marketed by the company KRONOS.

[0148] 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 is likely to form through 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.

[0149] Examples include IRGANOX ® 1010, IRGANOX ® B561, IRGANOX ® 245, IRGAFOS ® 168, TINUVIN® 328 or TINUVIN™ 770 marketed by BASF.

[0150] According to a preferred embodiment, the two-component composition according to the invention does not comprise peroxide.

[0151] According to a preferred embodiment, the two-component composition according to the invention does not include a quaternary ammonium salt such as, for example, dilauryldimethylammonium chloride or dodecyltrimethylammonium chloride.

[0152] In the composition according to the invention, the volume ratio 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, which was not feasible with peroxide: tertiary amine systems. B. Ready-to-use kit

[0153] The present invention also relates to a ready-to-use kit, comprising component A as defined above on the one hand and component B as defined above on the other hand, packaged in two separate compartments. It may, for example, be a two-component cartridge.

[0154] Indeed, the composition according to the invention can be found in a two-component form, for example in a ready-to-use kit, comprising component A on the one hand in a first compartment or drum and component B on the other hand in a second compartment or drum, in proportions adapted for a direct mixing of the two components, for example using a dosing pump.

[0155] According to one embodiment of the invention, the kit further comprises 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. C. Uses of the composition

[0156] 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.

[0157] The invention also relates to the use of said composition for the repair and / or structural or semi-structural bonding of materials, for example in the field of transport, automotive (car, bus or truck), assembly, marine, electronics, or construction.

[0158] The present invention relates to a method for assembling two substrates by bonding, comprising: - the mixture of components A and B as defined above to form the composition as defined above; - the coating on at least one of the two substrates to be assembled of said composition; - the effective contact of the two substrates; then - cross-linking of the composition.

[0159] 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.

[0160] Suitable substrates are, for example, inorganic substrates such as concrete, metals or alloys (such as aluminium alloys, steel, non-ferrous metals and galvanised metals); or organic substrates such as wood, plastics such as PVC, polycarbonate, PMMA, polyethylene, polypropylene, polyesters, epoxy resins; metal substrates and paint-coated composites.

[0161] Crosslinking can be carried out under electromagnetic irradiation, for example with a UV radiation source or with an LED. Electromagnetic irradiation can be carried out on the edges of the bond in the case of an opaque substrate or directly through the substrate in the case of a transparent substrate.

[0162] 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.

[0163] The inventors have advantageously discovered that the open time can be varied, in particular by varying different parameters such as the nature or content of the organic copper derivative(s) and / or sulfinate(s). The presence of a PI photoinitiator and / or exposure to electromagnetic irradiation also advantageously reduces the open time.

[0164] Furthermore, the compositions advantageously exhibit rapid cohesion growth, regardless of the open time (short in the electronics field, or long in the wind energy field). In addition, the compositions according to the invention advantageously exhibit good adhesive properties and advantageously result in tack-free surfaces after bonding.

[0165] The composition according to the invention is advantageously suited for transport compared to peroxide-based compositions.

[0166] The present invention also relates to a method for determining the crosslinking of a crosslinkable two-component composition as defined above, comprising a step of mixing components A and B as defined above.

[0167] All embodiments defined above for the crosslinkable two-component composition and components A and B apply to the present method.

[0168] The mixing step can be carried out for a period of 30 seconds to 1 minute.

[0169] During the initial mixing of components A and B, the composition is advantageously colored, particularly blue when the organic copper derivative is an organic copper(II) derivative; this notably allows verification that the mixture of parts A and B is homogeneous. During the crosslinking step, the composition advantageously changes color.

[0170] This change in the color of the composition advantageously allows monitoring and determination of when the composition polymerizes / crosslinks. This beneficial effect eliminates the need for additional coloring agents and allows verification by simple visual observation that the mixture is effective and that polymerization / crosslinking is occurring, thus facilitating implementation for end users.

[0171] All the embodiments described above can be combined with each other. In particular, the various aforementioned components of the composition, and especially the preferred modes, of the composition can be combined with each other.

[0172] 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%.

[0173] The invention is now described in the following embodiment examples which are given purely for illustrative purposes, and should not be interpreted to limit its scope. EXAMPLES

[0174] The following ingredients were used:

[0175] - SR® 506 D: isobomyl acrylate (IBOA) (CAS No.: 5888-33-5) marketed by ARKEMA;

[0176] - SR® 531: cyclic trimethylolpropane form acrylate (CAS No.: 66492-51-1) marketed by ARKEMA;

[0177] - Cu(Acac)2: copper(II) acetylacetonate (CAS No. 13395-16-9) available from SIGMA ALDRICH;

[0178] - Cu(3FAA)2: anhydrous copper(II) trifluoroacetate (CAS No.: 123333-88-0) available from SIGMA ALDRICH;

[0179] - Sodium p-toluene sulfinate (CAS No.: 824-79-3) available from SIGMA ALDRICH;

[0180] - 2FAA: difluoroacetic acid (CAS No.: 381-73-7) available from SIGMA ALDRICH.

[0181] Example 1: preparation of composition no. 1 (according to the invention)

[0182] 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.

[0183] 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.

[0184] [Tables 1] Composition No. 1 according to invention Component A Component B ingredients % by weight (relative to the total weight of A) ingredients % by weight (relative to the total weight of B) SR®531 97.5 SR®531 99 Cu(Acac)2 0.5 Sodium p-toluene sulfinate 1 2FAA 2 TOTAL 100 TOTAL 100

[0185] Component A and component B are mixed, in a volume ratio 1:1 using a Sulzer® mixpac mixer at an ambient temperature of 23°C.

[0186] Example 2: preparation of composition no. 2 (according to the invention)

[0187] 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.

[0188] 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.

[0189] [Tables2] Composition No. 2 according to invention Component A Component B ingredients % by weight (relative to the total weight of A) ingredients % by weight (relative to the total weight of B) SR®506D 97.5 SR®506D 99 Cu(Acac)2 0.5 Sodium p-toluene sulfinate 1 2FAA 2 TOTAL 100 TOTAL 100

[0190] Component A and component B are mixed, in a volume ratio 1:1 using a Sulzer® mixpac mixer at an ambient temperature of 23°C.

[0191] Example 3: preparation of composition no. 3 (according to the invention)

[0192] 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.

[0193] 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.

[0194] [Tables3] Composition No. 3 according to invention Component A Component B ingredients % by weight (relative to the total weight of A) ingredients % by weight (relative to the total weight of B) SR®531 99 SR®531 99 Cu(3FAA)2 1 Sodium p-toluene sulfinate 1 TOTAL 100 TOTAL 100

[0195] Component A and component B are mixed, in a volume ratio 1:1 using a Sulzer® mixpac mixer at an ambient temperature of 23°C. Example 4: Composition performance Measuring responsiveness:

[0196] The exotherm is continuously analyzed using a pyrometer and thermal imaging.

[0197] Peak time is the time required to reach the peak temperature (maximum of the exotherm observed during polymerization) as opposed to gel time (or latency time) which is the time it takes for the sample to begin to polymerize.

[0198] The time / temperature profiles were obtained using an Omega OS552-V1-6 industrial infrared thermometer (Omega Engineering®, Inc., Stamford, CT) with an accuracy of ± 1 °C for 2 g (approximately 4.0 mm height) and 0.25 g (1.4 mm height) of polymerization.

[0199] Bonding test:

[0200] Deposition of composition no. 1, no. 2 or no. 3 (obtained respectively in examples 1, 2 or 3) by mixing components A and B with a Sulzer® mixpac mixer) on a first glass microscope slide (25 x 76 mm);

[0201] - Display of a 2nd glass microscope slide (25 x 76 mm) on the 1st slide having received composition no. 1, no. 2 or no. 3

[0202] - Step of sliding the two microscope slides to allow distribution equal of composition n°1, n°2 or n°3 between the two slides (exposure to oxygen is reduced here).

[0203] The bonding time is the time after which it is no longer possible to separate the two blades.

[0204] [Tables4] Composition Peak time (s) Peak temperature (°C) Bonding time (s) Remarks Composition No. 1 (Example 1) 2 min 12 s 140°C 3 min no tack Composition No. 2 (Example 2) 3 min 30 s 140°C 5 min No tack Composition No. 3 (Example 3) 2 min 38 s 120°C No tack

[0205] nd: not determined

[0206] The peak times of compositions No. 1, No. 2 and No. 3 according to the invention are advantageously short and the exothermicity is significant, characterizing a good reactivity (improved cohesion). Bonding times are also short and the surfaces are free of residual tack.

Claims

1.

2. Demands Two-component, crosslinkable composition comprising: - a component A comprising: • a non-halogenated organic copper derivative; • a halogenated carboxylic acid; • at least one (meth)acrylate compound Ml; - a component B comprising at least one compound having the following formula (VI): [Ra-SO2 ]p, Qp+ (VI) in which: - Ra represents an aryl or heteroaryl radical, said heteroaryl and aryl possibly being substituted by at least one of the following radicals: F, OH, C(O)OMe, NHC(O)Me, methyl (Me), CF3 OH or SO2; - Q represents Li, Na, K or Zn, preferably Na or K; - p represents 1 or 2. Composition according to claim 1, characterized in that the organic copper derivative is selected from the group consisting of a copper salt of formula (VII-1) or a copper complex of formula (VII-2): (VII-2) in which: - R and R” each represent, independently of each other, an alkyl radical, a cycloalkyl radical, an aryl radical, a heteroaryl radical,; - R' represents a hydrogen atom, an alkyl radical, a cycloalkyl radical, an aryl radical, a heteroaryl radical, or R and R' (or R' and R”) which may also be involved in a single ring comprising 5 to 8 carbon atoms, said cycle possibly comprising at least one heteroatom (such as for example O, S); - R'” represents an alkyl radical, a cycloalkyl radical, an aryl radical, a heteroaryl radical.

3. Composition according to any one of claims 1 or 2, characterized in that the organic copper derivative is a copper salt of formula (VII-1) in which 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.

4. Composition according to any one of claims 1 or 2, characterized in that the organic copper derivative is a copper salt of formula (VII-2) in which: - R represents an alkyl radical, a cycloalkyl radical, an aryl radical, a heteroaryl radical, preferably an alkyl radical; - R' represents a hydrogen; - R' ' represents an alkyl radical.

5. Composition according to any one of claims 1 to 4, characterized in that the total content of organic copper derivative(s) ranges from 0.05% to 5% by weight, preferably from 0.1% to 2% by weight, and even more preferably from 0.2% to 1% by weight relative to the total weight of the crosslinkable two-component composition.

6. Composition according to any one of claims 1 to 5, characterized in that the halogenated carboxylic acid is selected from monohalogenated (comprising one halogen atom), dihalogenated (comprising two halogen atoms) or trihalogenated (comprising three halogen atoms) carboxylic acids.

7. Composition according to any one of claims 1 to 6, characterized in that the halogenated carboxylic acid is selected from the group consisting of monochloroacetic acid, monofluoroacetic acid, dichloroacetic acid, difluoroacetic acid, trichloroacetic acid, trifluoroacetic acid, and mixtures thereof, the halogenated carboxylic acid preferably being selected from dichloroacetic acid, difluoroacetic acid and mixtures thereof.

8. Composition according to any one of claims 1 to 7, characterized in that the total content of carboxylic acid(s)

9.

10. halogenated(s) ranges from 0.5% to 20% by weight, preferably from 0.5% to 10% by weight, and even more preferably from 0.5% to 2% by weight relative to the total weight of the crosslinkable two-component composition. Composition according to any one of claims 1 to 8, characterized in that the (meth)acrylate compound Ml is a (meth)acrylate monomer, an (meth)acrylate oligomer or a (meth)acrylate polymer. Composition according to any one of claims 1 to 9, characterized in that compound Ml has the following formula (F):

11. in which: - R1 represents H or methyl; - G represents an organic radical, G being preferably chosen from the group consisting of alkyls, cycloalkyls, alkenyls, cycloalkenyls, alkylaryls, arylalkyls or aryls, said alkyls, cycloalkyls, alkenyls, cycloalkenyls, alkylaryls, arylalkyls and aryls being possibly substituted, for example, substituted by an alkyl or a hydroxyl. Composition according to any one of claims 1 to 10, characterized in that compound Ml has one of the following formulas (I), (II), (III), (IV) or (V): in which: - R1 represents H or methyl; - R2 represents H, methyl or ethyl; - p represents 0 or 1; and - Z represents H, O, S, an alkyl group, a benzyl group, an aryl group, or an alkoxy group; - Y represents O, S, NH or CH2; ÿ;is a single bond or a double bond, provided that when Z represents O, then the bond ^^j is a double bond;

12. - G' is chosen from the group consisting of alkyls, cycloalkyls, alkenyls, cycloalkenyls, alkylaryls, arylalkyls or aryls, said alkyls, cycloalkyls, alkenyls, cycloalkenyls, alkylaryls, arylalkyls and aryls being possibly substituted by an alkyl group, said group G' being characterized in that it does not comprise a heteroatom; - G' is an alkyl substituted with an OH group. Composition according to claim 11, characterized in that in formula (I), G' is selected from the group consisting of C20 to C4 alkyls, preferably C20 to C4 alkyls, cycloalkyls, or aryls,

13. said alkyls, cycloalkyls, and aryls being optionally substituted by an alkyl group, said group G being characterized in that it does not comprise a heteroatom. Composition according to any one of claims 1 to 12, characterized in that: - Compounds of formula (I) are selected from methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-butyl (meth)acrylate, heptyl (meth)acrylate, 2-tert-butylheptyl (meth)acrylate, octyl (meth)acrylate, 3-isopropylheptyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, 5-methylundecyl (meth)acrylate, dodecyl (meth)acrylate, 2-methyldodecyl (meth)acrylate, tridecyl (meth)acrylate, 5-methyltridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, 2-methylhexadecyl (meth)acrylate, (meth)acrylate heptadecyl, 5-isopropylheptadecyl (meth)acrylate, 4-tert-butyloctadecyl (meth)acrylate, 5-ethyloctadecyl (meth)acrylate, 3-isopropyloctadecyl (meth)acrylate, octadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate,bornyl (meth)crylate, 2,3,4,5-tetra-t-butylcyclohexyl (meth)acrylate; benzyl (meth)acrylate, phenyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, isobornyl (meth)acrylate, and mixtures thereof; - Compounds of formula (II) are chosen from the following monomers: (II-A) (II-B) (II-C) - Compounds of formula (III) are chosen from the following monomers:

14.

15. (III-A) (III-B) (III-E) (III-F) - The compounds of formula (V) are selected from hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate. Composition according to any one of claims 1 to 13, characterized in that the total content of compound(s) (meth)acrylate Ml in component A is greater than or equal to 5% by weight, preferably greater than or equal to 20% by weight, even more preferably greater than or equal to 50% by weight, and even more advantageously greater than or equal to 70% by weight relative to the total weight of said component A. Composition according to any one of claims 1 to 14, characterized in that the compound of formula (VI) is selected from the following compounds: the compound of formula (VI) being preferably chosen from the following compounds:

16. Composition according to any one of claims 1 to 15, characterized in that it comprises at least one additive selected from the group consisting of catalysts, fillers, antioxidants, polymerization inhibitors, light stabilizers / UV absorbers, metal deactivators, antistatics, anti-hazing agents, foaming agents, biocides, plasticizers, lubricants, emulsifiers, colorants, pigments, rheological agents, impact modifiers, adhesion promoters, accelerators, optical brighteners, flame retardants, anti-seepage agents, nucleating agents, solvents, and mixtures thereof.

17. Composition according to claim 16, characterized in that the charge is an electrically or thermally conductive charge.

18. Ready-to-use kit, comprising component A as defined according to any one of claims 1 to 17 on the one hand and component B as defined according to any one of claims 1 to 17 on the other hand, packaged in two separate compartments.

19. Use of a crosslinkable two-component composition as defined according to any one of claims 1 to 17, as an adhesive, sealant or coating, preferably as an adhesive.

20. A method for assembling two substrates by bonding, comprising: • mixing components A and B as defined according to any one of claims 1 to 17 to form the composition as defined according to any one of claims 1 to 17; • coating at least one of the two substrates to be assembled with said composition; • effectively bringing the two substrates into contact; and then • crosslinking the composition.

21. Method for determining the crosslinking of a crosslinkable two-component composition as defined according to any one of claims 1 to 17, comprising a step of mixing components A and B as defined according to any one of claims 1 to 17, characterized in that during the initial mixing of components A and B the composition is colored, and during the crosslinking step, the composition changes color.