Compositions based on (meth) acrylate compounds

Abstract

The invention relates to a crosslinkable two-component composition and also to the use thereof, comprising:-a component A comprising:-an organocopper derivative; at least one (meth) acrylate compound M1; with the proviso that when the organocopper 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).

Description

Field of the Invention

[0001] The present invention relates to compositions based on (meth)acrylate compounds.

[0002] The invention also relates to the use of said composition in the repair and / or semistructural or structural bonding of materials, for example in the transport, marine, assembly, electronics or construction sectors. Technical Background

[0003] Acrylic compositions are known reactive systems which crosslink by free radical polymerization. They are used as adhesives, binders and coatings. Free radical polymerization is usually initiated by redox systems which lead to the generation of free radicals by means of redox reactions.

[0004] Most acrylic systems are two-component systems. The first component conventionally contains a reducing agent and a reactive monomer, and the second component contains an oxidizing agent. Once the two components have been mixed, the reducing agent induces the cleavage of the OO bond of, for example, an organic peroxide, and initiates polymerization.

[0005] Most current acrylic systems use peroxide / amine coupling to initiate the redox reaction. However, these systems suffer from several drawbacks, including stability issues, poor reactivity, particularly long open times, lack of versatility, etc.

[0006] There is a need for new compositions that allow one or more of these deficiencies to be at least partially overcome.

[0007] There is a particular need for novel compositions which have a high reactivity (high adhesion enhancement) independent of the associated open time.

[0008] A. Composition

[0009] The present invention relates to a crosslinkable two-component composition comprising:

[0010] - Component A comprising:

[0011] ·Organic copper derivatives;

[0012] at least one (meth)acrylate compound M1;

[0013] Provided that, when the organic copper derivative of component A is not halogenated, component A further comprises a halogenated carboxylic acid;

[0014] - component B, which comprises at least one compound of the following formula (VI):

[0015] [R a -SO 2 - ] p , Qp+ (VI)

[0016] in:

[0017] -R a represents an aryl or heteroaryl group, wherein the heteroaryl group and the aryl group are optionally substituted by at least one of the following groups: F, OH, C(O)OMe, NHC(O)Me, methyl (Me), CF 3 , OH or SO 2 - ;

[0018] -Q represents Li, Na, K or Zn, preferably Na or K;

[0019] -p stands for 1 or 2.

[0020] In the context of the present invention, the term "alkyl" denotes a hydrocarbon-based straight-chain or branched group which preferably contains 1 to 20 carbon atoms. Mention may be made, for example, of methyl, ethyl and propyl.

[0021] In the context of the present invention, the term "C4-C20 alkyl" means a straight-chain or branched alkyl group containing 4 to 20 carbon atoms.

[0022] In the context of the present invention, the term "alkenyl" denotes a hydrocarbon-based straight-chain or branched radical comprising at least one double bond, said radical preferably comprising 2 to 20 carbon atoms. Examples that may be mentioned include propenyl and butenyl.

[0023] In the context of the present invention, the term "alkynyl" denotes a hydrocarbon-based straight-chain or branched group comprising at least one triple bond, said group preferably containing 2 to 20 carbon atoms.

[0024] In the context of the present invention, the term "aryl" denotes a monocyclic aromatic group or a bicyclic aromatic group, which preferably contains 6 to 12 carbon atoms. Mention may be made, for example, of phenyl.

[0025] In the context of the present invention, the term "aralkyl" denotes an alkyl group substituted by an aryl group, the aralkyl group preferably containing 7 to 20 carbon atoms. As aralkyl group there may be mentioned, for example, benzyl.

[0026] In the context of the present invention, the term "alkaryl" denotes an aryl group substituted by an alkyl group, said alkaryl group preferably comprising 7 to 20 carbon atoms.

[0027] In the context of the present invention, the term "heteroaryl" means a monocyclic aromatic group or a bicyclic aromatic group which contains at least one heteroatom, such as O, S or N, and preferably contains 4 to 12 carbon atoms. Examples which may be mentioned include furanyl, thienyl, pyrrolyl, pyridyl, indolyl or imidazolyl.

[0028] In the context of the present invention, the term "cycloalkyl" denotes a mono- or polycyclic (preferably mono- or bicyclic) saturated system, which preferably comprises 3 to 12 carbon atoms, which rings may be bridged or fused in pairs, for example cyclopropyl, cyclopentyl, cyclohexyl or norbornyl.

[0029] In the context of the present invention, the term "heterocycloalkyl" denotes a monocyclic or polycyclic (preferably monocyclic or bicyclic) saturated system, which preferably comprises 3 to 12 carbon atoms and at least one heteroatom (eg O or N), which rings may be fused in pairs or bridged.

[0030] In the context of the present invention, the term "cycloalkenyl" denotes a monocyclic or polycyclic ring system comprising at least one double bond and preferably comprising 3 to 12 carbon atoms, which rings may be fused in pairs or bridged.

[0031] In the context of the present invention the term "alkoxy" denotes an -O-alkyl group.

[0032] Component A

[0033] Organic copper derivatives

[0034] The composition according to the invention comprises an organic copper derivative, preferably an organic copper(II) derivative.

[0035] The organocopper derivative may be halogenated or non-halogenated. Preferably, the organocopper derivative is non-halogenated.

[0036] The organic copper derivative may be selected from a copper salt of formula (VII-1) or a copper complex of formula (VII-2):

[0037]

[0038] in:

[0039] - R and R" independently of one another each represent alkyl, cycloalkyl, aryl or heteroaryl, said alkyl, cycloalkyl, aryl and heteroaryl being optionally substituted by one or more halogen atoms, for example one or more fluorine atoms;

[0040] -R' represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heteroaryl group,

[0041] Alternatively, R and R' (or R' and R") may also be joined in the same ring containing 5-8 carbon atoms, which ring optionally contains at least one heteroatom (such as O or S); -R"' represents an alkyl group, a cycloalkyl group, an aryl group or a heteroaryl group, which is optionally substituted by one or more halogen atoms, such as one or more fluorine atoms.

[0042] Among the copper salts of formula (VII-1), there can be mentioned, for example, copper(II) acetate (e.g., anhydrate or monohydrate), copper(II) monofluoroacetate, copper(II) difluoroacetate, copper(II) trifluoroacetate (e.g., anhydrate or monohydrate), copper(II) hexanoate, copper(II) ethyl-2-hexanoate, and mixtures thereof.

[0043] According to a preferred embodiment, in formula (VII-1), R'' represents an alkyl group containing 1 to 20 carbon atoms (preferably 1 to 7 carbon atoms), which is optionally substituted by one or more halogen atoms, such as one or more fluorine atoms.

[0044] Among the copper complexes of formula (VII-2), mention may be made of, for example, copper(II) hexafluoroacetylacetonate (Cu(hfacac) 2 ), copper(II) trifluoroacetylacetonate (Cu(tfacac) 2 ), copper(II) acetylacetonate (Cu(acac) 2 ) and bis(2-acetylcyclohexanone)copper(II), which have the following formulae respectively:

[0045]

[0046] According to a preferred embodiment, in formula (VII-2):

[0047] -R represents an alkyl group, a cycloalkyl group, an aryl group or a heteroaryl group, preferably an alkyl group;

[0048] -R' represents hydrogen;

[0049] -R" represents an alkyl group optionally substituted by one or more halogen atoms, for example one or more fluorine atoms.

[0050] The organic copper derivative is preferably a copper complex of formula (VII-2), and more particularly copper(II) acetylacetonate (Cu(acac) 2 ).

[0051] The total content of organic copper derivatives (especially of formula (VII-1) or (VII-2)) 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.

[0052] Halogenated carboxylic acids

[0053] According to the invention, when the organic copper derivative of component A as defined above is not halogenated, component A further comprises a halogenated carboxylic acid.

[0054] It should be noted that when the organocopper derivative is halogenated, then component A may optionally comprise a halogenated carboxylic acid.

[0055] The halocarboxylic acid may be selected from a monohalocarboxylic acid (containing one halogen atom), a dihalocarboxylic acid (containing two halogen atoms) or a trihalocarboxylic acid (containing three halogen atoms).

[0056] The halogenated carboxylic acid may be selected from the group consisting of monochloroacetic acid, monofluoroacetic acid, dichloroacetic acid, difluoroacetic acid, trichloroacetic acid, trifluoroacetic acid, and mixtures thereof.

[0057] Preferably, the halocarboxylic acid is selected from dichloroacetic acid, difluoroacetic acid and mixtures thereof.

[0058] When halocarboxylic acids are present, the total content of halocarboxylic acids may range from 0.5% to 20%, preferably from 0.5% to 10% and even more preferably from 0.5% to 2% by weight relative to the total weight of the crosslinkable two-component composition.

[0059] (Meth)acrylate compound M1

[0060] Component A comprises at least one (meth)acrylate compound M1.

[0061] The (meth)acrylate compound M1 may be a (meth)acrylate monomer, a (meth)acrylate oligomer, or a (meth)acrylate polymer.

[0062] Preferably, the (meth)acrylate compound M1 is a (meth)acrylate monomer.

[0063] The (meth)acrylate compound M1 may have the following formula (F):

[0064]

[0065] in:

[0066] -R 1 represents H or methyl;

[0067] -G represents an organic group.

[0068] Preferably, G is selected from alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkaryl, aralkyl or aryl, optionally substituted by, for example, alkyl or hydroxy.

[0069] The (meth)acrylate compound M1 may have one of the following formulae (I), (II), (III), (IV) or (V):

[0070]

[0071] in:

[0072] -R 1 represents H or methyl;

[0073] -R 2 represents H, methyl or ethyl;

[0074] -p represents 0 or 1; and

[0075] -Z represents H, O, S, alkyl, benzyl, aryl or alkoxy;

[0076] -Y represents O, S, NH or CH 2 ;

[0077] is a single bond or a double bond,

[0078] The condition is that when Z represents O, then the key It is a double bond;

[0079] -G' is selected from alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkaryl, aralkyl or aryl, wherein the alkyl,

[0080] Cycloalkyl, alkenyl, cycloalkenyl, alkaryl, aralkyl and aryl are optionally substituted with alkyl, and the G'

[0081] The radical is characterized in that it does not contain any heteroatoms;

[0082] -G" is an alkyl group substituted with an OH group.

[0083] In the above formula (I), G' can be selected from C1-C20 alkyl (preferably C4-C20 alkyl), cycloalkyl, alkenyl, cycloalkenyl, alkaryl, aralkyl or aryl, and the alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkaryl, aralkyl and aryl are optionally substituted by alkyl, and the group G' is characterized in that it does not contain any heteroatoms.

[0084] In the above formula (I), G' is preferably selected from alkyl (preferably C1-C20 and even more preferably C4-C20), cycloalkyl or aryl, the alkyl, cycloalkyl and aryl being optionally substituted by alkyl, the group G' being characterized in that it does not contain any heteroatoms. Also preferably, G' is selected from cycloalkyl.

[0085] Among the cycloalkyl radicals, mention may be made, for example, of isobornyl, tert-butylcyclohexyl, trimethylcyclohexyl, dicyclopentenyl and tricyclodecanyl.

[0086] Among the compounds of formula (I), mention may be made, for example, of 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)acrylate, 2,3,4,5-tetra-tert-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.

[0087] Preferred compounds of formula (I) M1 are as follows:

[0088]

[0089] Among the compounds M1 of the above-mentioned formula (II), there may be mentioned, for example, the following monomers:

[0090]

[0091] Among the compounds M1 of the above-mentioned formula (III), there may be mentioned, for example, the following monomers:

[0092]

[0093] Among the compounds M1 of formula (II) or formula (III), the following monomers and mixtures thereof are preferred:

[0094]

[0095] Among the compounds M1 of formula (V), mention may be made, for example, of hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate.

[0096] The total content of (meth)acrylate compounds M1 in component A may be greater than or equal to 5 wt %, preferably greater than or equal to 20 wt %, even more preferably greater than or equal to 50 wt %, and even more advantageously greater than or equal to 70 wt %, relative to the total weight of component A.

[0097] The content of the (meth)acrylate compound M1 in the crosslinkable two-component composition according to the invention, relative to the total weight of the crosslinkable two-component composition, can range from 5% by weight to 99% by weight, preferably from 20% by weight to 99% by weight, even more preferably from 50% by weight to 99% by weight, and even more advantageously from 75% by weight to 99% by weight.

[0098] The (meth)acrylate monomer M1 may or may not be a recycled monomer.

[0099] Photoinitiator P1 (optional)

[0100] Component A may also comprise a photoinitiator P1.

[0101] The photoinitiator may be any photoinitiator known to those skilled in the art. Under the action of UV-visible radiation, the photoinitiator generally produces a group responsible for initiating the photopolymerization reaction and in particular allows to improve the efficiency of the photopolymerization reaction. Needless to say, the choice of the photoinitiator varies with the light source used (according to its ability to effectively absorb the selected radiation). For example, a suitable photoinitiator may be selected based on its UV-visible absorption spectrum. Advantageously, the photoinitiator is suitable for working with a radiation source emitting in the near (ultraviolet) region of 300nm-420nm. Advantageously, the UV or visible radiation source may be an LED.

[0102] The photoinitiator P1 can be selected from:

[0103] - Type I photoinitiator selected from:

[0104] - Acetophenone and alkoxyacetophenone families, such as 2,2-dimethoxy-2-phenylacetophenone and 2-diethyl-2-phenylacetophenone;

[0105] -Hydroxyacetophenone family, such as 2,2-dimethyl-2-hydroxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone and 2-hydroxy-4'-(2-hydroxypropoxy)-2-methylpropiophenone;

[0106] - the alkylaminoacetophenone family, such as 2-methyl-4′-(methylthio)-2-morpholinopropiophenone, 2-benzyl-2-(dimethylamino)-4-morpholinobutyrophenone and 2-(4-methylbenzyl)-2-(dimethylamino)-4-morpholinobutyrophenone;

[0107] - the benzoin ether family, such as benzil, benzoin methyl ether and benzoin isopropyl ether;

[0108] - the phosphine oxide family, 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-trimethylphenylphosphine oxide (BAPO);

[0109] -Metallocene family, such as ferrocene, bis(η 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluoro)-3-(1H-pyrrol-1-yl)phenyl)titanium and cumylcyclopentadienyl iron hexafluorophosphate;

[0110] - Type II photoinitiator selected from:

[0111] - the benzophenone family, for example 4-phenylbenzophenone, 4-(4′-methylphenylthio)benzophenone and 1-[4-[(4-benzoylphenyl)thio]phenyl]-2-methyl-2-[(4-methylphenyl)sulfonyl]-1-propanone;

[0112] - the thioxanthone family, such as isopropylthioxanthone (ITX), 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2-chlorothioxanthone and 1-chloro-4-isopropylthioxanthone;

[0113] -benzoylformate family, such as methyl benzoylformate;

[0114] - the dibenzylidene ketone family, for example p-dimethylaminoketone;

[0115] - the coumarin family, such as 5-methoxycoumarin and 7-methoxycoumarin, 7-diethylaminocoumarin and N-phenylglycine coumarin;

[0116] - photoinitiators from the dye family, 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 and rhodamines;

[0117] - and mixtures thereof.

[0118] According to a preferred embodiment, the photoinitiator P1 is selected from:

[0119] - the phosphine oxide family, 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-trimethylphenylphosphine oxide (BAPO);

[0120] - the thioxanthone family, such as isopropylthioxanthone (ITX), 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2-chlorothioxanthone and 1-chloro-4-isopropylthioxanthone;

[0121] Even more preferably, the photoinitiator P1 is chosen from diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO) and ethyl(2,4,6-trimethylbenzoyl)phenylphosphine oxide (TPO-L).

[0122] The total content of photoinitiator P1 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.

[0123] If a photoinitiator is present in the two-component composition according to the invention, the photoinitiator content may be greater than or equal to 0.01 wt %, for example greater than or equal to 0.1 wt %, relative to the total weight of the composition.

[0124] Component B

[0125] Compound of formula (VI)

[0126] Component B comprises at least one compound having the following formula (VI):

[0127] [R a -SO 2 - ] p , Q p+ (VI)

[0128] in:

[0129] -R a represents an aryl or heteroaryl group, wherein the heteroaryl group and the aryl group are optionally substituted by at least one of the following groups: F, OH, C(O)OMe, NHC(O)Me, methyl (Me), CF 3 , OH or SO 2 - ;

[0130] -Q represents Li, Na, K or Zn, preferably Na or K;

[0131] -p stands for 1 or 2.

[0132] The compound of formula (VI) may be selected from the following compounds:

[0133]

[0134]

[0135] According to a preferred embodiment, the compound of formula (VI) is selected from the following compounds:

[0136]

[0137] The total content of compounds 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.

[0138] (Meth)acrylate compounds

[0139] Component B may comprise one or more (meth)acrylate compounds M1 as defined for component A.

[0140] Preferably, component B comprises the same (meth)acrylate compound M1 as in component A.

[0141] Component B may comprise more than 5% by weight of compound M1, preferably more than 20% by weight, advantageously more than 50% by weight, preferably even more than 70% by weight and even more preferably more than 90% by weight, relative to the total weight of component B.

[0142] Component B may comprise, in particular, 60% to 99.9% by weight of compound M1, relative to the total weight of component B, and preferably 80% to 99.5% by weight.

[0143] Preferably, the (meth)acrylate compound M1 of component B does not contain any acid group. The acid group can 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 compound M1 in component B is not 10-methacryloyloxydecyl dihydrogenphosphate.

[0144] Composition

[0145] The crosslinkable two-component composition according to the invention may contain at least one additive selected from the group consisting of catalysts, fillers, antioxidants, polymerization inhibitors, light stabilizers / UV absorbers, metal deactivators, antistatic agents, antifogging agents, foaming agents, biocides, plasticizers, lubricants, emulsifiers, colorants, pigments, rheological agents, impact modifiers, adhesion promoters, accelerators, fluorescent whitening agents, flame retardants, barrier agents, nucleating agents, solvents, and mixtures thereof.

[0146] These additives may be present in component A and / or in component B of the composition according to the invention.

[0147] As examples of plasticizers that can be used, mention may be made of any plasticizer commonly used in the adhesives field, for example epoxy resins, phthalates, benzoates, trimethylolpropane esters, trimethylolethane esters, trimethylolmethane esters, glycerides, pentaerythritol esters, naphthenic mineral oils, adipates, cyclohexyl dicarboxylates, paraffin oils, natural oils (optionally epoxidized), polypropylene, polybutene, hydrogenated polyisoprene, and mixtures thereof.

[0148] For example, you can use:

[0149] - diisodecyl phthalate, for example sold by BASF under the name Palatinol TM DIDP Sales,

[0150] - Phenol esters of alkylsulfonic acids, for example those marketed by the company Lanxess under the name Sale,

[0151] -Diisononyl 1,2-cyclohexanedicarboxylate, for example, is available from BASF under the name Hexamoll Sale,

[0152] - pentaerythritol tetravalerate, for example from the company Perstorp under the name Pevalen TM Sale,

[0153] - Epoxidized soybean oil, for example sold under the name Arkema 7170 sales.

[0154] As examples of rheological (thixotropic) agents that can be used, mention may be made of any rheological agent commonly used in the field of adhesive compositions.

[0155] Preferably, the thixotropic agent is selected from:

[0156] PVC plastisols, which correspond to suspensions of PVC in plasticizers 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,

[0157] - pyrogenic silica, for example manufactured by Wacker under the name N20 sales;

[0158] - Urea derivatives, which result from the reaction of aromatic diisocyanate monomers (eg 4,4′-MDI) with aliphatic amines (eg butylamine).

[0159] The preparation of such urea derivatives is described in particular in patent application FR 1 591 172;

[0160] - micronized amide waxes, such as those sold by Arkema SLT or SLA.

[0161] The composition according to the invention may also comprise at least one organic and / or inorganic filler.

[0162] The inorganic fillers that can be used are advantageously selected so as to improve the mechanical properties of the composition according to the invention in the crosslinked state.

[0163] As examples of usable inorganic fillers, any inorganic filler commonly used in the field of adhesive compositions can be used. These fillers are generally in the form of particles with various geometric shapes. For example, their shape can be spherical, fibrous or irregular.

[0164] Preferably, the filler is selected from clay, quartz, carbonate fillers, kaolin, gypsum, and mixtures thereof; preferably, the filler is selected from carbonate fillers, such as alkali metal carbonates or alkaline earth metal carbonates, and more preferably calcium carbonate or chalk.

[0165] These fillers may be untreated or treated, for example with an organic acid, for example stearic acid or a mixture of organic acids formed predominantly from stearic acid.

[0166] Inorganic hollow microspheres may also be used, such as glass hollow microspheres, and more particularly those prepared from sodium calcium borosilicate or sodium calcium aluminosilicate.

[0167] The filler may be electrically and / or thermally conductive.

[0168] Among the electrically conductive fillers, mention may be made, for example, of carbon black, graphite, carbon fibers, metal M' optionally coated with a metal M" layer, inorganic or organic fillers coated with a metal layer, and mixtures thereof.

[0169] Among the metals coated with a metal layer, mention may be made, for example, of copper coated with a silver layer.

[0170] The organic filler may be coated with a metal layer, for example silver or copper. Mention may be made, for example, of polymethyl methacrylate (PPMA) coated with a silver layer.

[0171] Among the thermally conductive fillers, mention may be made of, for example, carbon black powder, graphite, carbon fibers (CNT), metal oxides, metal hydroxides, metal silicates, metal sulfides, boron nitride and aluminum nitride. The metal of the metal compound is selected, for example, from tin, indium, antimony, aluminum, titanium, iron, magnesium, zinc, etc. The electrically conductive filler and / or thermally conductive filler may be in the form of spherical particles, tubes, flakes or fibers, in particular having a range of 0.01 m 2 / g-100m 2 / g specific surface area.

[0172] Preferably, the composition comprises a conductive filler.

[0173] The composition according to the invention may comprise from 0% to 95% by weight and preferably from 40% to 95% by weight of one or more electrically conductive fillers and / or thermally conductive fillers, relative to the total weight of the composition.

[0174] Preferably, electrically conductive fillers and / or thermally conductive fillers are in component B of the composition.

[0175] The composition according to the invention may also comprise at least one adhesion promoter, which is preferably selected from silanes, such as aminosilanes, epoxysilanes or acrylsilanes; or adhesion promoters based on phosphates, such as 2-hydroxyethyl methacrylate phosphate, 2-methacryloyloxyethyl phosphate, bis(2-methacryloyloxyethyl)phosphate, 2-acryloyloxyethyl phosphate, bis(2-acryloyloxyethyl)phosphate, methyl(2-methacryloyloxyethyl)phosphate, ethyl(2-methacryloyloxyethyl)phosphate, 2-hydroxyethyl methacrylate monophosphate and mixtures of diphosphates.

[0176] When the pigment is present in the composition, the content of the pigment is preferably less than or equal to 3 wt%, and more preferably less than or equal to 2 wt%, relative to the total weight of the composition. When the pigment is present, the pigment may, for example, account for 0.1 wt%-3 wt% or 0.4 wt%-2 wt%, relative to the total weight of the composition.

[0177] The pigment may be an inorganic pigment or an organic pigment.

[0178] For example, the pigment is TiO 2 , especially those sold by Kronos 2059.

[0179] The composition may contain at least one UV stabilizer or antioxidant in an amount of 0.1 wt% to 3 wt%, preferably 1 wt% to 3 wt%. These compounds are generally introduced to protect the composition from degradation caused by 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.

[0180] Examples which may be mentioned include the 1010, B561, 245. 168. 328 or Tinuvin TM 770.

[0181] According to a preferred embodiment, the two-component composition according to the invention does not contain any peroxides.

[0182] According to a preferred embodiment, the two-component composition according to the invention does not comprise any quaternary ammonium salts, such as, for example, dilauryldimethylammonium chloride or dodecyltrimethylammonium chloride.

[0183] In the composition according to the invention, the component A / component B volume ratio may range from 20 / 1 to 1 / 1, preferably from 10 / 1 to 1 / 1. The A / B volume ratio is preferably 1 / 1, which is not possible for peroxide / tertiary amine systems.

[0184] B. Ready-to-use kit

[0185] The 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. This may be, for example, a two-component cartridge.

[0186] In particular, 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 cartridge and component B on the other hand in a second compartment or cartridge, in proportions suitable for direct mixing of the two components (for example with the aid of a metering pump).

[0187] According to one embodiment of the present invention, the kit further comprises one or more means for mixing component A and component B. Preferably, the mixing means are selected from metering pumps, static mixers, having a diameter suitable for the amount used.

[0188] C. Use of the Composition

[0189] The invention also relates to the use of a crosslinkable two-component composition as defined above as an adhesive, a mastic or a coating, preferably as an adhesive.

[0190] The invention also relates to the use of said composition in the structural or semi-structural repair and / or bonding of materials, for example in the transport, motor vehicle (car, bus or truck), assembly, marine, electronics or construction sectors.

[0191] The present invention relates to a method for assembling two substrates by bonding, comprising:

[0192] - mixing component A and component B as defined above to form a composition as defined above;

[0193] - coating at least one of the two substrates to be assembled with said composition;

[0194] - placing the two substrates in operative contact; and then

[0195] - crosslinking the composition.

[0196] The cross-linking step may be carried out at a temperature between 0°C and 200°C, preferably between 10°C and 150°C, preferably between 23°C and 80°C and especially between 20°C and 25°C.

[0197] Suitable substrates are, for example, inorganic substrates, such as concrete, metals or alloys (for example aluminium alloys, steel, non-ferrous metals and galvanized metals); or organic substrates, such as wood, plastics (for example PVC), polycarbonate, PMMA, polyethylene, polypropylene, polyesters, epoxy resins; metal substrates and painted composite materials.

[0198] The crosslinking can be carried out under electromagnetic radiation, for example using a UV radiation source or an LED. The electromagnetic radiation can be carried out on the bonding edge (in the case of opaque substrates) or directly through the substrate (in the case of transparent substrates).

[0199] The cross-linking step under electromagnetic radiation may be carried out at a wavelength greater than 300 nm, preferably ranging from 360 nm to 680 nm and even more preferably from 360 nm to 420 nm.

[0200] The inventors have advantageously found that the open time can be significantly varied by varying different parameters such as the nature or content of the organocopper derivative and / or the sulfinate. The presence of a photoinitiator P1 and / or exposure to electromagnetic radiation also advantageously results in a reduction of the open time.

[0201] Furthermore, the composition advantageously shows a rapid adhesion build-up regardless of the open time (short in the electronics field, or long in the wind power field). Furthermore, the composition according to the invention advantageously shows good adhesive properties and advantageously results in a tack-free surface after bonding.

[0202] Compared to peroxide-based compositions, the compositions according to the invention are advantageously suitable for transportation.

[0203] The invention also relates to a method for determining the crosslinking of a crosslinkable two-component composition as defined above, comprising the step of mixing component A and component B as defined above.

[0204] All embodiments defined above for the crosslinkable two-component composition and also for component A and component B apply to the present process.

[0205] The mixing step may be performed for a time ranging from 30 seconds to 1 minute.

[0206] During the initial mixing of components A and B, the composition is advantageously coloured, in particular blue when the organocopper derivative is an organocopper(II) derivative; this makes it possible in particular to check that the mixture of parts A and B is homogeneous. During the crosslinking step, the composition advantageously changes colour.

[0207] This change in the color of the composition advantageously makes it possible to monitor and determine when the composition is polymerized / crosslinked. This advantageous effect makes it possible to avoid the use of additional colorants and verify by simple visual observation that mixing is effective and polymerization / crosslinking is effective, thereby facilitating use by the end user.

[0208] All embodiments described above can be combined together. In particular, the various above-mentioned components of the composition, and in particular the preferred aspects of the composition, can be combined together.

[0209] In the context of the present invention, the term "between x and y" or "in the range of xy" denotes an interval comprising the upper and lower limits x and V. For example, the range "between 0% and 25%" particularly includes the values ​​0% and 25%.

[0210] The present invention is now described in the following examples, which are given for illustrative purposes only and should not be construed as limiting the scope of the present invention. Example

[0211] Use the following ingredients:

[0212] - 506D: isobornyl acrylate (IBOA) sold by Arkema (CAS No.: 5888-33-5);

[0213] - 531: Cyclic trimethylolpropane formal acrylate sold by Arkema (CAS No.: 66492-51-1);

[0214] -Cu(acac) 2 : Copper(II) acetylacetonate from Sigma-Aldrich (CAS No.: 13395-16-9);

[0215] -Cu(3FAA) 2 : Anhydrous copper(II) trifluoroacetate from Sigma-Aldrich (CAS No.: 123333-88-0);

[0216] - sodium p-toluenesulfinate from Sigma-Aldrich (CAS No.: 824-79-3);

[0217] -2FAA: difluoroacetic acid from Sigma-Aldrich (CAS No.: 381-73-7).

[0218] Embodiment 1: Preparation of Composition 1 (according to the invention)

[0219] The ingredients of component A were mixed in the proportions indicated in the table below in a mixer maintained under constant stirring and under air at a temperature of 23°C.

[0220] The various ingredients constituting component B were mixed in the proportions indicated in the table below in a mixer maintained under constant stirring and under air at a temperature of 23°C.

[0221] [Table 1]

[0222]

[0223]

[0224] use Component A and component B were mixed in a volume ratio of 1:1 using a Mixpac mixer at room temperature of 23°C.

[0225] Example 2 : Preparation of composition 2 (according to the invention)

[0226] The ingredients of component A were mixed in the proportions indicated in the table below in a mixer maintained under constant stirring and under air at a temperature of 23°C.

[0227] The various ingredients constituting component B were mixed in the proportions indicated in the table below in a mixer maintained under constant stirring and under air at a temperature of 23°C.

[0228] [Table 2]

[0229]

[0230] use Component A and component B were mixed in a volume ratio of 1:1 using a Mixpac mixer at room temperature of 23°C.

[0231] Example 3 : Preparation of composition 3 (according to the invention)

[0232] The ingredients of component A were mixed in the proportions indicated in the table below in a mixer maintained under constant stirring and under air at a temperature of 23°C.

[0233] The various ingredients constituting component B were mixed in the proportions indicated in the table below in a mixer maintained under constant stirring and under air at a temperature of 23°C.

[0234] [Table 3]

[0235]

[0236] use Component A and component B were mixed in a volume ratio of 1:1 using a Mixpac mixer at room temperature of 23°C.

[0237] Example 4 : Properties of the composition

[0238] Reactivity measurement :

[0239] The exotherm was continuously analyzed using a pyrometer and by thermal imaging.

[0240] Peak time is the time required to reach peak temperature (maximum exotherm found during polymerization), in contrast to pot life (or lag time), which is the time required for a sample to begin to polymerize.

[0241] The Omega OS552-V1-6 industrial infrared thermometer was used with an accuracy of ±1°C. Inc., Stamford, CT) generated time / temperature curves for the polymerization of 2 g (approximately 4.0 mm height) and 0.25 g (1.4 mm height).

[0242] Adhesion test :

[0243] - Composition 1, 2 or 3 (in Example 1, 2 or 3, respectively, by using Mixpac mixer to mix component A and component B) deposited on a first microscope glass slide (25 x 76 mm);

[0244] - fixing a second microscope glass slide (25 x 76 mm) on the first slide receiving composition 1, 2 or 3;

[0245] - Slide the two microscope slides so that composition 1, 2 or 3 is evenly distributed between the two slides (reduced oxygen exposure here).

[0246] The bonding time is the time after which it is no longer possible to separate the two slides.

[0247] stability :

[0248] - A bottle containing 10 g of component A and a bottle containing 10 g of component B (from one of compositions 1, 2 or 3) were closed and placed in an oven at 40°C under air.

[0249] • 1.5 g of each component was collected weekly using a pipette and placed in the two compartments of a medmix mixpac dual cartridge mixer (Sulzer).

[0250] • Once mixed, reactivity was routinely monitored using the equipment described above for measuring peak time.

[0251] The formulation was declared unstable when the peak time was no longer observed, whereas the peak time was observed at an earlier time.

[0252] [Table 4]

[0253]

[0254] nd = not determined

[0255] The peak times of compositions 1, 2 and 3 according to the invention are advantageously short and the exotherm is high, indicating good reactivity (adhesion enhancement). The bonding time is also short and there is no residual tack on the surface.

Claims

1. A crosslinkable two-component composition comprising: - Component A comprising: ·Organic copper derivatives; at least one (meth)acrylate compound M1; Provided that, when the organic copper derivative of component A is not halogenated, component A further comprises a halogenated carboxylic acid; - component B, which comprises at least one compound of the following formula (VI): [R a -SO2 - ] p ,Q p+ (VI) in: -R a represents an aryl or heteroaryl group, wherein the heteroaryl and aryl groups are optionally substituted by at least one of the following groups: 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 stands for 1 or 2.

2. A composition as claimed in claim 1, characterized in that The organic copper derivative is selected from a copper salt of formula (VII-1) or a copper complex of formula (VII-2): in: - R and R" independently of one another each represent alkyl, cycloalkyl, aryl or heteroaryl, said alkyl, cycloalkyl, aryl and heteroaryl being optionally substituted by one or more halogen atoms, for example one or more fluorine atoms; -R' represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heteroaryl group, Alternatively, R and R' (or R' and R") may also be joined in the same ring containing 5 to 8 carbon atoms, said ring optionally containing at least one heteroatom (eg O or S); -R"' represents an alkyl, cycloalkyl, aryl or heteroaryl group, which is optionally substituted by one or more halogen atoms, such as one or more fluorine atoms.

3. A composition as claimed in any one of claims 1 and 2, characterized in that The organocopper derivative is a copper salt of formula (VII-1), wherein R'' represents an alkyl group containing 1-20 carbon atoms, preferably 1-7 carbon atoms, which is optionally substituted by one or more halogen atoms, such as one or more fluorine atoms.

4. A composition as claimed in any one of claims 1 and 2, characterized in that The organic copper derivative is a copper salt of formula (VII-2), wherein: -R represents an alkyl group, a cycloalkyl group, an aryl group or a heteroaryl group, preferably an alkyl group; -R' represents hydrogen; -R" represents an alkyl group optionally substituted by one or more halogen atoms, for example one or more fluorine atoms.

5. A composition as claimed in any one of claims 1 to 4, characterized in that The organic copper derivative of component A is not halogenated.

6. A composition as claimed in any one of claims 1 to 5, characterized in that The total content of the organic copper derivative 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.

7. A composition as claimed in any one of claims 1 to 6, characterized in that The halogenated carboxylic acid is selected from a monohalogenated (containing one halogen atom) carboxylic acid, a dihalogenated (containing two halogen atoms) carboxylic acid or a trihalogenated (containing three halogen atoms) carboxylic acid.

8. A composition as claimed in any one of claims 1 to 7, characterised in that The halogenated carboxylic acid is selected from monochloroacetic acid, monofluoroacetic acid, dichloroacetic acid, difluoroacetic acid, trichloroacetic acid, trifluoroacetic acid, and mixtures thereof, and the halogenated carboxylic acid is preferably selected from dichloroacetic acid, difluoroacetic acid, and mixtures thereof.

9. A composition as claimed in any one of claims 1 to 8, characterised in that When halocarboxylic acid is present, the total content of halocarboxylic acid ranges from 0.5% to 20%, preferably from 0.5% to 10% and even more preferably from 0.5% to 2% by weight relative to the total weight of the crosslinkable two-component composition.

10. A composition as claimed in any one of claims 1 to 9, characterised in that The (meth)acrylate compound M1 is a (meth)acrylate monomer, a (meth)acrylate oligomer or a (meth)acrylate polymer.

11. A composition as claimed in any one of claims 1 to 10, characterised in that Compound M1 has the following formula (F): in: -R 1 represents H or methyl; -G represents an organic group, G is preferably selected from alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkaryl, aralkyl or aryl, wherein the alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkaryl, aralkyl and aryl groups are optionally substituted, for example, by alkyl or hydroxyl groups.

12. A composition as claimed in any one of claims 1 to 11, characterised in that Compound M1 has one of the following formulae (I), (II), (III), (IV) or (V): in: -R 1 represents H or methyl; -R 2 represents H, methyl or ethyl; -p represents 0 or 1; and -Z represents H, O, S, alkyl, benzyl, aryl or alkoxy; -Y represents O, S, NH or CH2; - is a single bond or a double bond, The condition is that when Z represents O, then the key It is a double bond; -G' is chosen from alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkaryl, aralkyl or aryl, said alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkaryl, aralkyl and aryl being optionally substituted by alkyl, said G' group being characterized in that it does not contain any heteroatoms; -G" is an alkyl group substituted with an OH group.

13. A composition as claimed in claim 12, characterized in that In formula (I), G' is selected from C1-C20 and preferably C4-C20 alkyl, cycloalkyl or aryl, said alkyl, cycloalkyl and aryl being optionally substituted by alkyl, said group G' being characterized in that it does not contain any heteroatoms.

14. A composition as claimed in any one of claims 1 to 13, characterized in that: - the compound of formula (I) is 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, 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)acrylate, 2,3,4,5-tetra-tert-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; - The compound of formula (II) is selected from the following monomers: - The compound of formula (III) is selected from the following monomers: - The compound of formula (V) is selected from hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate.

15. A composition as claimed in any one of claims 1 to 14, characterised in that Relative to the total weight of component A, the total content of (meth)acrylate compounds M1 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.

16. A composition as claimed in any one of claims 1 to 15, characterised in that The compound of formula (VI) is selected from the following compounds: The compound of formula (VI) is preferably selected from the following compounds:

17. A composition as claimed in any one of claims 1 to 16, characterised in that It contains at least one additive selected from the following: catalysts, fillers, antioxidants, polymerization inhibitors, light stabilizers / UV absorbers, metal deactivators, antistatic agents, antifogging agents, foaming agents, biocides, plasticizers, lubricants, emulsifiers, colorants, pigments, rheological agents, impact modifiers, adhesion promoters, accelerators, fluorescent whitening agents, flame retardants, anti-seepage agents, nucleating agents, solvents, and mixtures thereof.

18. A composition as claimed in claim 17, characterized in that The filler is an electrically conductive filler or a thermally conductive filler.

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

20. Use of a crosslinkable two-component composition as defined in any one of claims 1 to 18 as an adhesive, a glue or a coating material, preferably as an adhesive.

21. A method of assembling two substrates by bonding, comprising: ○ mixing component A and component B as defined in any one of claims 1 to 18 to form a composition as defined in any one of claims 1 to 18; o coating at least one of the two substrates to be assembled with the composition; o placing the two substrates in operative contact; and then ○ The composition is crosslinked.

22. A method for determining the crosslinking of a crosslinkable two-component composition as defined in any one of claims 1 to 18, comprising the step of mixing component A and component B as defined in any one of claims 1 to 18, characterized in that During the initial mixing of component A and component B, the composition is pigmented, and during the cross-linking step, the composition changes color.

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