Composition based on (METH)acrylate compounds

Abstract

The present invention relates to a crosslinkable two-component composition comprising: - a component A comprising: * an organic copper derivative; * at least one (meth) acrylate compound M1; * a compound having the following formula (X): P(O)(ORb)(ORc)(ORd) - a component B comprising at least one compound having the following formula (VI): Formula (VI), said crosslinkable two-component composition being characterized in that the total content of compound(s) of formula (X) ranges from 0.1% to 20% by weight relative to the total weight of said composition.

Description

[0001] Composition based on (meth)acrylate compounds

[0002] FIELD OF THE INVENTION

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

[0004] The invention also relates to the use of said composition for the repair and / or semi-structural or structural bonding of materials, for example in the fields of transport, marine, assembly, electronics or construction.

[0005] TECHNOLOGICAL BACKGROUND

[0006] Acrylic compositions are known reactive systems that crosslink by free radical polymerization. They are used as adhesives, sealants, and coatings. Free radical polymerization is typically initiated by a redox system that, through an oxidation-reduction reaction, leads to the production of radicals.

[0007] Most acrylic systems are two-component systems. The first component traditionally contains the reducing agent and reactive monomers, and the second component contains the oxidizing agent. Once the two components are mixed, the reducing agent induces the cleavage of the 0-0 bond of the organic peroxide, for example, and initiates polymerization.

[0008] Most current acrylic systems use peroxide / amine pairs to initiate the redox reaction. However, these systems suffer from several drawbacks such as stability problems, low reactivity with long open times, a lack of versatility, etc.

[0009] There is a need for new compositions that can at least partially overcome one or more of these drawbacks.

[0010] In particular, there is a need for new compositions with high reactivity (high cohesion increase), regardless of the associated open time.

[0011] A. Composition

[0012] The present invention relates to a crosslinkable two-component composition comprising:

[0013] - a component A comprising:

[0014] • an organic copper derivative;

[0015] • at least one (meth)acrylate compound; • a compound of the following formula (X): P(O)(OR b )(GOLD c )(GOLD d ), in which R b R c , R d , identical or different, is chosen from hydrogen, alkyl, aryl, heteroaryl, alkenyl, cycloalkyl, said alkyl, aryl, heteroaryl, alkenyl, cycloalkyl, being optionally substituted;

[0016] - a component B comprising:

[0017] - at least one compound having the following formula (VI): in which:

[0018] - R a represents an aryl or heteroaryl radical, said heteroaryl and aryl being optionally substituted by at least one of the following radicals: F, OH, C(O)OMe, NHC(O)Me, methyl (Me), CF3, OH or SO2';

[0019] - Q represents Li, Na, K or Zn, preferably Na or K;

[0020] - p represents 1 or 2;

[0021] - optionally at least one (meth)acrylate compound; said crosslinkable two-component composition being characterized in that the total content of compound(s) of formula (X) ranges from 0.1% to 20% by weight relative to the total weight of said composition.

[0022] In the context of the invention, the term "alkyl" means a linear or branched hydrocarbon radical preferably comprising from 1 to 20 carbon atoms. Examples that may be mentioned are methyl, ethyl, propyl.

[0023] In the context of the invention, the term “C4 to C20 alkyl” means a linear or branched alkyl comprising from 4 to 20 carbon atoms.

[0024] In the context of the invention, the term "alkenyl" means a linear or branched hydrocarbon radical comprising at least one double bond, said radical preferably comprising from 2 to 20 carbon atoms. By way of example, mention may be made of propenyl and butenyl.

[0025] In the context of the invention, the term “alkynyl” means a linear or branched hydrocarbon radical comprising at least one triple bond, said radical preferably comprising from 2 to 20 carbon atoms.

[0026] In the context of the invention, the term "aryl" means a monocyclic or bicyclic aromatic radical preferably comprising from 6 to 12 carbon atoms. For example, phenyl may be mentioned. In the context of the invention, the term "arylalkyl" means an alkyl group substituted by an aryl group, the arylalkyl group preferably comprising from 7 to 20 carbon atoms. As an arylalkyl group, for example, benzyl may be mentioned.

[0027] In the context of the invention, the term "alkylaryl" means an aryl group substituted by an alkyl group, said alkylaryl group preferably comprising from 7 to 20 carbon atoms.

[0028] In the context of the invention, the term "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 that may be mentioned are furanyl, thiophenyl, pyrrolyl, pyridinyl, indolyl or imidazolyl radicals.

[0029] In the context of the invention, the term "cycloalkyl" means a monocyclic or polycyclic system, preferably mono or bicyclic, saturated, preferably comprising from 3 to 12 carbon atoms, the rings possibly being two by two fused or bridged, such as cyclopropyl, cyclopentyl, cyclohexyl or norbornyl groups.

[0030] In the context of the invention, the term "heterocycloalkyl" means a monocyclic or polycyclic system, preferably mono or bicyclic, saturated, preferably comprising from 3 to 12 carbon atoms and at least one heteroatom such as for example O or N, the rings possibly being two by two fused or bridged.

[0031] In the context of the invention, the term "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 two by two fused or bridged.

[0032] In the context of the invention, the term “alkoxy” means an -O-alkyl radical.

[0033] Component A

[0034] Organic copper derivative

[0035] The composition according to the invention comprises an organic copper derivative, preferably an organic copper (II) derivative.

[0036] The organic copper derivative may be halogenated or non-halogenated. Preferably, the organic copper derivative is non-halogenated.

[0037] The organic copper derivative may be selected from the group consisting of a copper salt of formula (VI 1-1) or a copper complex of formula (VII-2): in which:

[0038] - R and R” each represents, independently of one another, 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;

[0039] - 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”) may also be engaged in a single cycle comprising from 5 to 8 carbon atoms, said cycle possibly comprising at least one heteroatom (such as for example O, S);

[0040] - R'” represents 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.

[0041] Among the copper salts of formula (VI 1-1 ), we can for example cite 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.

[0042] According to a preferred embodiment, in formula (VI 1-1), 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.

[0043] Among the copper complexes of formula (VII-2), we can cite for example copper (II) hexafluoroacetylacetonate (Cu(hfacac)2), copper (II) trifluoroacetylacetonate (Cu(tfacac)2), copper (II) acetylacetonate (Cu(acac)2) and copper (II) bis(2-acetylcyclohexanonate), respectively having the following formulas:

[0044] According to a preferred embodiment, in formula (VI 1-2):

[0045] - R represents an alkyl radical, a cycloalkyl radical, an aryl radical, a heteroaryl radical, preferably an alkyl radical;

[0046] - R' represents hydrogen;

[0047] - R” represents an alkyl radical optionally substituted by one or more halogen atoms, such as for example one or more fluorine atoms.

[0048] The organic copper derivative is preferably a copper complex of formula (VII-2) and more particularly copper (II) acetylacetonate (Cu(acac)2).

[0049] The total content of organic copper derivative(s), and in particular of formula (VII-1) or (VII-2) can range from 0.03% to 10% by weight, preferably from 0.1% to 2% by weight, and even more preferably from 0.1% to 1% by weight relative to the total weight of the crosslinkable two-component composition.

[0050] Compound of formula (X)

[0051] Preferably, in the compounds of formula (X), at least one of R b , R c , R d represents a hydrogen.

[0052] Preferred compounds of formula (X) are those in which:

[0053] - at least one of R b ' R c , R d represents H;

[0054] - at least one of R b ' R c , R drepresents an alkyl, said alkyl being optionally substituted.

[0055] The substituents may be selected from halogen, alkyl, aryl, amino, hydroxyl, -OC(=O)-C(R e )=CH2 with R e representing H or CH3. The compounds of formula (X) are preferably chosen from the group consisting of: phosphoric acid, 2-hydroxyethyl phosphate esters of methacrylate such as, for example, 2-(methacryloyloxy)ethyl phosphate and bis[2-(methacryloyloxy)ethyl] phosphate, 2-hydroxyethyl phosphate esters of acrylate such as, for example, 2-(acryloyloxy)ethyl phosphate and bis-[2-(acryloyloxy)ethyl] phosphate, 2-ethylhexyl phosphate esters such as, for example, 2-(ethylhexyl) phosphate and bis[2-(ethylhexyl)] phosphate, and mixtures thereof.

[0056] The compounds of formula (X) are preferably chosen from the group consisting of: phosphoric acid, 2-(methacryloyloxy)ethyl phosphate, bis[2-(methacryloyloxy)ethyl] phosphate, 2-(acryloyloxy)ethyl phosphate, bis-[2-(acryloyloxy)ethyl] phosphate, (2-ethylhexyl) phosphate, bis(2-ethylhexyl) phosphate, and mixtures thereof.

[0057] Even more preferably, the compounds of formula (X) are chosen from the group consisting of bis[2-(methacryloyloxy)ethyl] phosphate, bis(2-ethylhexyl) phosphate and mixtures thereof.

[0058] Compounds of formula (X) can be marketed, for example, from Sigma-Aldrich.

[0059] Preferably, the total content of compound(s) of formula (X) ranges from 0.5% to 10% by weight, and more preferably from 1% to 2% by weight relative to the total weight of said composition.

[0060] (Meth)acrylate compound

[0061] Component A comprises at least one (meth)acrylate compound.

[0062] The (meth)acrylate compound may be a (meth)acrylate monomer, a (meth)acrylate oligomer, or a (meth)acrylate polymer.

[0063] Preferably, the (meth)acrylate compound is a (meth)acrylate monomer.

[0064] The (meth)acrylate compound may have the following formula (F): in which: - R 1 represents H or methyl;

[0065] - G represents an organic radical.

[0066] Preferably, G is selected 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.

[0067] The (meth)acrylate compound may have one of the following formulas (I), (II), (III), (IV) or (V): in which:

[0068] - R 1 represents H or methyl;

[0069] - R 2 represents H, methyl or ethyl;

[0070] - p represents 0 or 1; and

[0071] - Z represents H, O, S, an alkyl group, a benzyl group, an aryl group, or an alkoxy group;

[0072] - Y represents O, S, NH or CH2;

[0073] - is a single bond or a double bond, provided that when Z represents O, then the bond is a double bond; - G' is selected 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 by an alkyl group, said group G' being characterized in that it does not comprise a heteroatom;

[0074] - G” is an alkyl substituted by an OH group.

[0075] In the above-mentioned formula (I), G' may 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.

[0076] In the above-mentioned formula (I), G' is preferably selected from the group consisting of alkyls (preferably C1 to C20, and even more preferably C4-C20), cycloalkyls, arylalkyls, or aryls, said alkyls, cycloalkyls, arylalkyls and aryls being optionally substituted by an alkyl group, said group G' being characterized in that it does not comprise a heteroatom. More preferably, G' is selected from cycloalkyls and arylalkyls.

[0077] Among the cycloalkyls, we can cite for example isobornyl, tert-butyl cyclohexyl, trimethylcyclohexyl, dicyclopentenyl, tricyclodecyl.

[0078] 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, (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 (metha)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. Preferred compounds of formula (I) are:, and benzylmethacrylate. Among the compounds of formula (II) mentioned above, the following monomers may be mentioned, for example: Among the compounds of formula (III) mentioned above, the following monomers may be mentioned, for example:

[0079] (lll-C) (lll-D)

[0080] (Ill-E) (Hl-F)

[0081] Among the compounds of formulas (II) or (III), the following monomers and their mixtures are preferred:

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

[0083] Preferably, the (meth)acrylate compound is chosen from:

[0084] - compounds of formula (III);

[0085] - compounds of formula (V).

[0086] More preferably, the (meth)acrylate compound is chosen from:

[0087] - benzyl(meth)acrylate,

[0088] - hydroxyethyl(meth)acrylate,

[0089] - the compound (lll-F) above,

[0090] - compound (ll-A) above,

[0091] - compound (I ll-A) above; and mixtures thereof. The total content of (meth)acrylate compound(s) in component A may be greater than or equal to 20% by weight, preferably greater than or equal to 50% by weight, and even more preferably greater than or equal to 70% by weight relative to the total weight of said component A.

[0092] The content of (meth)acrylate compound(s) in the crosslinkable two-component composition according to the invention may range from 5% to 99.95% 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.

[0093] The (meth)acrylate monomer can be a recycled monomer or not.

[0094] The (meth)acrylate compound can be partially or totally bio-sourced.

[0095] Halogenated carboxylic acid (optional)

[0096] The composition may further comprise a halogenated carboxylic acid.

[0097] The halogenated carboxylic acid may be selected from monohalogenated (comprising one halogen atom), dihalogenated (comprising two halogen atoms) or trihalogenated (comprising three halogen atoms) carboxylic acids.

[0098] 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.

[0099] Preferably, the halogenated carboxylic acid is chosen from dichloroacetic acid, difluoroacetic acid and mixtures thereof.

[0100] When present, the total content of halogenated carboxylic acid(s) may 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.

[0101] Photoinitiator P1 (optional)

[0102] Component A may further comprise a photoinitiator P1.

[0103] The photoinitiator may be any photoinitiator known to those skilled in the art. Under the action of UV-visible radiation, the photoinitiator typically generates radicals which will be responsible for initiating the photopolymerization reaction, and in particular makes it possible to increase the efficiency of the photopolymerization reaction. This is of course chosen according to the light source used, depending on its capacity to effectively absorb the selected radiation. For example, the appropriate photoinitiator may be chosen based on its UV-visible absorption spectrum. Advantageously, the photoinitiator is suitable for working with irradiation sources emitting in the near region ranging from 300 to 420 nm. Advantageously, the source of the UV or visible radiation may be an LED.

[0104] Photoinitiator P1 can be chosen from the group consisting of:

[0105] - type I photoinitiators chosen from:

[0106] - the family of acetophenones and alkoxyacetophenones, such as for example 2,2-dimethoxy-2-phenylacetophenone and 2-diethyl-2-phenylacetophenone;

[0107] - the family of hydroxyacetophenones, 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;

[0108] - the family of alkylaminoacetophenones, 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;

[0109] - the family of benzoin ethers, such as for example benzyl, methyl benzoin ether and isopropyl benzoin ether;

[0110] - the family of phosphine oxides, such as for example diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), ethyl-(2,4,6-trimethylbenzoyl)phenylphosphine oxide (TPO-L) and bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylphenyl phosphine oxide (BAPO);

[0111] - the family of metallocenes, such as for example ferrocene, titanium bis(eta 5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro)-3-(1 H-pyrrole-1-yl)-phenyl) and iron (cumene)cyclopentadienyl hexafluorophosphate;

[0112] - type II photoinitiators chosen from:

[0113] - the benzophenone family, such as for example 4-phenylbenzophenone, 4-(4'-methylphenylthio)benzophenone, 1-[4[(4-benzoylphenyl)thio]phenyl]-2-methyl-2-[(4-methylphenyl)sulfonyl]-1-propanone;

[0114] - the thioxanthone family, such as for example isopropylthioxanthone (ITX), 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2-chlorothioxanthone and 1-chloro-4-isopropylthioxanthone;

[0115] - the family of benzoyl formate esters, such as for example methylbenzoylformate;

[0116] - the family of dibenzylidene ketones, such as for example p-dimethylaminoketone; - the family of coumarins, such as for example 5-methoxy and 7-methoxy coumarin, 7-diethylamino coumarin and N-phenylglycine coumarin;

[0117] - photoinitiators of the dye family such as, for example, triazines, fluorones, cyanines, safranins, 4,5,6,7-tetrachloro-3',6'-dihydroxy-2',4',5',7'-tetraiodo-3H-spiro[isobenzofuran-1,9'-xanthen]-3-one, pyrylium and thiopyrylium, thiazines, flavins, pyronins, oxazines, rhodamines;

[0118] - and their mixtures.

[0119] According to a preferred embodiment, the photoinitiator P1 is chosen from:

[0120] - the family of phosphine oxides, such as for example diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), ethyl-(2,4,6-trimethylbenzoyl)phenylphosphine oxide (TPO-L) and bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylphenyl phosphine oxide (BAPO);

[0121] - the thioxanthone family, such as for example isopropylthioxanthone (ITX), 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2-chlorothioxanthone and 1-chloro-4-isopropylthioxanthone; the photoinitiator P1 being even more preferably 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 it is present in the two-component composition according to the invention, the content of photoinitiator P1 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.

[0124] Component B

[0125] Compound of formula (VI)

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

[0127] [R a -SO2'] P , Q P+ (VI) in which:

[0128] - R arepresents an aryl or heteroaryl radical, said heteroaryl and aryl being optionally substituted by at least one of the following radicals: F, OH, C(O)OMe, NHC(O)Me, methyl (Me), CF3, OH or SO2';

[0129] - Q represents Li, Na, K or Zn, preferably Na or K; - p represents 1 or 2.

[0130] The compound of formula (VI) may be chosen from the following compounds: According to a preferred embodiment, the compound of formula (VI) is chosen from the following compounds:

[0131] The total content of compound(s) of formula (VI) as defined above may range from 0.05% to 10.0% 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.

[0132] (Meth)acrylate compounds

[0133] Component B may comprise one or more (meth)acrylate compound(s) as defined for component A.

[0134] The (meth)acrylate compound of component B may be the same as or different from the (meth)acrylate compound(s) of component A.

[0135] Preferably, component B comprises one or more (meth)acrylate compound(s).

[0136] Component B may comprise more than 5% by weight of (meth)acrylate compound(s), preferably more than 20% by weight, and advantageously more than 50% by weight of compound(s) M1, more preferably more than 70% by weight, and even more preferably more than 90% by weight, relative to the total weight of said component B.

[0137] Component B may in particular comprise from 60% to 99.9% by weight of (meth)acrylate compound(s), and preferably from 80% to 99.5% by weight, relative to the total weight of said component B.

[0138] Preferably, the (meth)acrylate compound of component B does not comprise 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 compound in component B is not 10-methacryloyloxydecyldihydrogen phosphate.

[0139] Preferably, the (meth)acrylate compound of component B is not a compound of formula (V) as defined above.

[0140] Preferably, the (meth)acrylate compound of component B is chosen from the compounds of formulas (I), (II) or (III) as defined above.

[0141] Composition

[0142] The crosslinkable two-component composition according to the invention may comprise at least one additive chosen from the group consisting of catalysts, fillers, antioxidants, polymerization inhibitors, light stabilizers / UV absorbers, metal deactivators, antistatics, antifogging agents, foaming agents, biocides, plasticizers, lubricants, emulsifiers, colorants, pigments, rheological agents, impact modifiers, adhesion promoters, accelerators, optical brighteners, flame retardants, anti-oozing agents, nucleating agents, solvents, and mixtures thereof.

[0143] These additives may be present in component A and / or component B of the composition according to the invention.

[0144] As an example of a plasticizing agent that can be used, mention may be made of any plasticizing agent usually used in the field of adhesives 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 (optionally epoxidized), polypropylenes, polybutylenes, hydrogenated polyisoprenes, and mixtures thereof.

[0145] For example, it is possible to use: diisodecyl phthalate, such as for example marketed under the name PALATINOL™ DI DP 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 ARKEMA.

[0146] As an example of a rheology agent (thixotropic) that can be used, we can cite any rheology agent usually used in the field of adhesive compositions.

[0147] 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 at temperatures ranging from 60°C to 80°C. These plastisols may be those described in particular in the work “Polyurethane Sealants”, Robert M. Evans, ISBN 087762-998-6, 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.

[0148] The composition according to the invention may further comprise at least one organic and / or mineral filler.

[0149] 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.

[0150] As an example of a usable mineral filler, any mineral filler commonly used in the field of adhesive compositions can be used. These fillers are typically in the form of particles of various geometries. They may, for example, be spherical, fibrous, or have an irregular shape.

[0151] 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 carbonate fillers, such as alkali or alkaline earth metal carbonates, and more preferably calcium carbonate or chalk.

[0152] These fillers may be untreated or treated, for example using an organic acid such as stearic acid, or a mixture of organic acids consisting predominantly of stearic acid.

[0153] Hollow mineral microspheres such as hollow glass microspheres, and more particularly those made of sodium and calcium borosilicate or aluminosilicate, can also be used.

[0154] The filler may be an electrically and / or thermally conductive filler. Examples of electrically conductive fillers include carbon black, graphite, carbon fibers, a metal M' optionally coated with a layer of metal M”, a mineral or organic filler coated with a layer of metal, and mixtures thereof.

[0155] Among the metals coated with a layer of metal, we can for example cite copper coated with a layer of silver.

[0156] Organic fillers can be coated with a layer of metal such as silver or copper. For example, polymethyl methacrylate (PPMA) coated with a layer of silver can be cited.

[0157] Examples of thermally conductive fillers include carbon black powders, graphite, carbon fibers (CNTs), metal oxides, metal hydroxides, metal silicates, metal sulfides, boron nitride, and aluminum nitride. The metals in the metal compounds are, for example, selected from tin, indium, antimony, aluminum, titanium, iron, magnesium, zinc, etc. Electrically and / or thermally conductive fillers may be in the form of spherical particles, tubes, flakes, or fibers, in particular having a specific surface area ranging from 0.01 m 2 / g at 100 m 2 / g.

[0158] Preferably, the composition comprises electrically conductive fillers.

[0159] 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 filler(s) relative to the total weight of said composition.

[0160] Preferably, the electrically and / or thermally conductive fillers are in component B of said composition.

[0161] The composition according to the invention may further comprise at least one adhesion promoter, preferably chosen from silanes, such as aminosilanes, epoxysilanes or acryloyl silanes.

[0162] When a pigment is present in the composition, its content is preferably less than or equal to 3% by weight, 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. The pigments may be organic or inorganic pigments.

[0163] For example, the pigment is TiC>2, in particular KRONOS® 2059 marketed by the KRONOS company.

[0164] The composition may comprise an amount of 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 which is likely to form by the action of heat or light. These compounds may include primary antioxidants which scavenge free radicals. The primary antioxidants may be used alone or in combination with other secondary antioxidants or UV stabilizers.

[0165] Examples include IRGANOX ® 1010, IRGANOX® B561, IRGANOX ® 245, IRGAFOS ® 168, TINUVIN® 328 or TINUVIN™ 770 marketed by BASF.

[0166] According to a preferred embodiment, the two-component composition according to the invention does not comprise peroxide.

[0167] According to a preferred embodiment, the two-component composition according to the invention does not comprise a quaternary ammonium salt such as, for example, dilauryldimethylammonium chloride or dodecyltrimethylammonium chloride.

[0168] According to a preferred embodiment, the two-component composition according to the invention does not comprise aromatic amines.

[0169] According to a preferred embodiment, the two-component composition according to the invention does not comprise a vanadium-based compound.

[0170] In the composition according to the invention, the volume ratio of component A / component B can range from 20 / 1 to 1 / 1, preferably from 10 / 1 to 1 / 1. The volume ratio A / B is preferably 1 / 1, which was not possible with peroxide:tertiary amine systems.

[0171] B. Ready-to-use kit

[0172] 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.

[0173] Indeed, the composition according to the invention may be in a two-component form, for example within 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 suitable for direct mixing of the two components, for example using a dosing pump.

[0174] 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

[0175] 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.

[0176] 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.

[0177] The present invention relates to a method for assembling two substrates by bonding, comprising: mixing components A and B as defined above to form the composition as defined above; coating at least one of the two substrates to be assembled with said composition; effectively bringing the two substrates into contact; then crosslinking the composition.

[0178] 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.

[0179] Suitable substrates are, for example, inorganic substrates such as concrete, metals or alloys (such as aluminum alloys, steel, non-ferrous metals and galvanized metals); or organic substrates such as wood, plastics such as PVC, polycarbonate, PMMA, polyethylene, polypropylene, polyesters, epoxy resins; metal substrates and paint-coated composites.

[0180] Crosslinking can be done under electromagnetic irradiation such as for example with a UV radiation source or with an LED. Electromagnetic irradiation can be carried out on the edges of the bonding in the case of an opaque substrate or directly through the substrate in the case of a transparent substrate.

[0181] The crosslinking step under electromagnetic irradiation can 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.

[0182] The inventors have advantageously discovered that the open time can be varied in particular by varying different parameters such as the nature or the content of organic copper derivative(s) and / or sulfinate(s) and / or the compound of formula (X). The presence of photoinitiator P1 and / or subjection to electromagnetic irradiation also advantageously makes it possible to reduce the open time.

[0183] Furthermore, the compositions advantageously exhibit a rapid increase in cohesion, regardless of the open time (short in the electronics field, or long in the wind power field). In addition, the compositions according to the invention advantageously exhibit good adhesive properties, and advantageously lead to tack-free surfaces after bonding.

[0184] The composition according to the invention is advantageously suitable for transport compared to peroxide-based compositions.

[0185] 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.

[0186] All of the embodiments defined above for the crosslinkable two-component composition as well as components A and B apply to the present method.

[0187] The mixing step can be carried out for a period of time ranging from 30 seconds to 1 minute.

[0188] During the initial mixing of components A and B, the composition is advantageously colored, in particular blue when the organic copper derivative is an organic copper (II) derivative, this makes it possible in particular to verify that the mixture of parts A and B is homogeneous. During the crosslinking step, the composition advantageously changes color.

[0189] This evolution of the color of the composition advantageously makes it possible to monitor and determine when the composition polymerizes / crosslinks. This advantageous effect makes it possible to avoid the use of additional coloring agents and to verify by simple visual observation that the mixture is effective and that the polymerization / crosslinking is effective, which facilitates implementation for end users.

[0190] All the embodiments described above may be combined with each other. In particular, the various aforementioned constituents of the composition, and in particular the preferred embodiments of the composition, may be combined with each other.

[0191] In the context of the invention, by "between x and y", or "ranging from x to y", is meant an interval in which the limits x and y are included. For example, the range "between 0% and 25%" includes in particular the values ​​0% and 25%. The invention is now described in the following exemplary embodiments which are given purely for illustrative purposes, and should not be interpreted to limit its scope.

[0192] EXAMPLES

[0193] The following ingredients were used:

[0194] - SR® 531: cyclic trimethylolpropane formal acrylate (CAS no.: 66492-51-1) marketed by ARKEMA;

[0195] - Cu(Acac)2: copper II acetylacetonate (CAS no.: 13395-16-9) available from SIGMA ALDRICH;

[0196] - Sodium p-toluene sulfinate (CAS No.: 824-79-3) available from SIGMA ALDRICH;

[0197] - mixture G comprising bis[2-(methacryloyloxy)ethyl] phosphate and 2-(methacryloyloxy)ethyl phosphate;

[0198] - MEP: Bis[2-(methacryloyloxy)ethyl] phosphate (CA: 32435-46-4) available from SIGMA-ALDRICH.

[0199] - EHP: Bis(2-ethylhexyl) phosphate (CAS: 298-07-7) available from SIGMA-ALDRICH;

[0200] - HEMA: 2-hydroxyethylmethacrylate;

[0201] - MA: methacrylic acid (CAS: 79-41-4) available from SIGMA-ALDRICH;

[0202] - Visiomer®BNMA: benzylmethacrylate marketed by EVONIK.

[0203] Example 1: preparation of composition no. 1 (according to the invention)

[0204] 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.

[0205] 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. [Table 1]

[0206] Component A and component B are mixed in a 1:1 volume ratio using a Sulzer® mixpac mixer at room temperature of 23°C.

[0207] Bonding test:

[0208] Depositing composition no. 1 by mixing components A and B with a Sulzer® mixpac mixer) on a 1 ère glass microscope slide (25 x 76 mm);

[0209] - Displaying a 2 ème glass microscope slide (25 x 76 mm) on the 1 èreblade having received composition no. 1

[0210] - Step of sliding the two microscope slides to allow an equal distribution of composition no. 1 between the two slides (exposure to oxygen is reduced here).

[0211] The bonding time is the time from which it is no longer possible to separate the two blades.

[0212] Finally, the bonding time is 30.0 min. The results advantageously show good adhesion with composition No. 1, without the use of aromatic amines or organic peroxides. Example 2: preparation of composition No. 2 (according to the invention)

[0213] 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.

[0214] In a mixer maintained under constant agitation and in air, the different ingredients constituting component B are mixed in the proportions indicated in the following table at a temperature of 23°C.

[0215] [Table 2]

[0216] Component A and component B are mixed in a 1:1 volume ratio using a Sulzer® mixpac mixer at room temperature of 23°C.

[0217] Example 3: preparation of composition no. 3 (according to the invention)

[0218] 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.

[0219] 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. [Table 3]

[0220] Component A and component B are mixed in a 1:1 volume ratio using a Sulzer® mixpac mixer at room temperature of 23°C.

[0221] Example 4: preparation of composition no. 4 (according to the invention)

[0222] 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.

[0223] 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. [Table 4] Component A and component B are mixed in a 1:1 volume ratio using a Sulzer® mixpac mixer at room temperature of 23°C.

[0224] Example 5: Performances of compositions #2, #3, and #4

[0225] Measurement of reactivity:

[0226] The exotherm is continuously analyzed using a pyrometer and thermal imaging.

[0227] Peak time is the time required to reach the peak temperature (maximum of the exotherm observed during polymerization).

[0228] Time / temperature profiles were performed 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.

[0229] The results are provided in the following table:

[0230] [Table 5] nd: not determined

[0231] Example 6: Performance of composition no. 2 with photoactivation

[0232] Photoactivation of Composition No. 2 (example 2) was carried out during the pyrometric measurement.

[0233] Photoactivation and Reactivity Measurement:

[0234] Photoactivation was performed with a 395 nm LED lamp (power 1 W / cm2), attached to the pyrometer. LED activation occurred for a maximum of 45 seconds, after which the time to peak exotherm was measured. Immediately after photoactivation, the sample temperature was below 40 °C. Tl

[0235] The exotherm is continuously analyzed using a pyrometer and thermal imaging.

[0236] Peak time is the time required to reach the peak temperature (maximum of the exotherm observed during polymerization).

[0237] Time / temperature profiles were performed 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.

[0238] Component A and component B are mixed in a 1:1 volume ratio using a Sulzer® mixpac mixer at room temperature of 23°C. The pyrometric results are provided in the following table:

[0239] [Table 6]

[0240] The results show that composition No. 2 crosslinks advantageously without the use of aromatic amines, peroxides, or halogenated compounds. Composition No. 2 crosslinks advantageously with or without actinic radiation (UV irradiation). With UV irradiation, the peak time decreases advantageously with the irradiation dose, indicating that the crosslinking rate increases with increasing said dose. The crosslinking rate can be advantageously controlled with the irradiation dose.

Claims

CLAIMS 1. Crosslinkable two-component composition comprising: - a component A comprising: • an organic copper derivative; • at least one (meth)acrylate compound; • a compound of the following formula (X): P(O)(OR b )(GOLD c )(GOLD d ), in which R b R c , R d , identical or different, is chosen from hydrogen, alkyl, aryl, heteroaryl, alkenyl, cycloalkyl, said alkyl, aryl, heteroaryl, alkenyl, cycloalkyl, being optionally substituted; - a component B comprising: - at least one compound having the following formula (VI): in which: - R a represents an aryl or heteroaryl radical, said heteroaryl and aryl being optionally substituted by at least one of the following radicals: F, OH, C(O)OMe, NHC(O)Me, methyl (Me), CF 3 , OH or SO2 ' ; - Q represents Li, Na, K or Zn, preferably Na or K; - p represents 1 or 2; - optionally at least one (meth)acrylate compound; said crosslinkable two-component composition being characterized in that the total content of compound(s) of formula (X) ranges from 0.1% to 20% by weight relative to the total weight of said composition.

2. Composition according to claim 1, characterized in that the organic copper derivative is chosen from the group consisting of a copper salt of formula (VI 1-1) or a copper complex of formula (VII-2): in which: - R and R” each represents, independently of one another, 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; - 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”) may also be engaged in a single cycle comprising from 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, 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.

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-2), preferably copper (II) acetylacetonate (Cu(acac)2).

4. Composition according to any one of claims 1 to 4, characterized in that the organic copper derivative of component A is not halogenated.

5. Composition according to any one of claims 1 to 4, characterized in that the (meth)acrylate compound is a (meth)acrylate monomer, a (meth)acrylate oligomer or a (meth)acrylate polymer.

6. Composition according to any one of claims 1 to 5, characterized in that the (meth)acrylate compound has the following formula (F): in which: - R 1 represents H or methyl; - G represents an organic radical, G preferably being 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.

7. Composition according to any one of claims 1 to 6, characterized in that the (meth)acrylate compound has one of the following formulas (I), (II), (III), (IV) or (V): in which: - R 1 represents H or methyl; - R 2 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; - is a single bond or a double bond, provided that when Z represents O, then the bond is a double bond; - G' is selected 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 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.

8. Composition according to any one of claims 1 to 7, characterized in that: - the compounds of formula (I) are chosen 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 (metha)acrylate, 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;, - the compounds of formula (II) are chosen from the following monomers: (ll-A) (HB) (HC) - the compounds of formula (III) are chosen from the following monomers: - the compounds of formula (V) are chosen from hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate.

9. Composition according to any one of claims 1 to 8, characterized in that the (meth)acrylate compound is chosen from: benzyl (meth)acrylate, hydroxyethyl (meth)acrylate, a compound (III-F), a compound (II-A), a compound (III-A), and mixtures thereof.

10. Composition according to any one of claims 1 to 9, characterized in that the compound of formula (VI) is chosen from the following compounds: the compound of formula (VI) being preferably chosen from the following compounds:

11. Composition according to any one of claims 1 to 10, characterized in that the compound of formula (X) is that in which at least one of R b ' R c , R d represents a hydrogen.

12. Composition according to any one of claims 1 to 11, characterized in that the compound of formula (X) is chosen from the group consisting of phosphoric acid, 2-(methacryloyloxy)ethyl phosphate, bis[2-(methacryloyloxy)ethyl] phosphate, 2-(acryloyloxy)ethyl phosphate, bis-[2-(acryloyloxy)ethyl] phosphate, (2-ethylhexyl) phosphate, bis(2-ethylhexyl) phosphate, and mixtures thereof.

13. Composition according to any one of claims 1 to 12, characterized in that the compound of formula (X) is chosen from the group consisting of bis[2-(methacryloyloxy)ethyl]phosphate, bis(2-ethylhexyl)phosphate and mixtures thereof.

14. Composition according to any one of claims 1 to 13, characterized in that it does not comprise peroxide.

15. Composition according to any one of claims 1 to 14, characterized in that it does not comprise an aromatic amine.

16. Composition according to any one of claims 1 to 15, characterized in that it does not comprise a vanadium-based compound.

17. Ready-to-use kit, comprising component A as according to any one of claims 1 to 16 on the one hand and component B as defined according to any one of claims 1 to 16 on the other hand, packaged in two separate compartments.

18. Use of a crosslinkable two-component composition as defined according to any one of claims 1 to 16, as an adhesive, sealant or coating, preferably as an adhesive.

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