COMPOSITION BASED ON (METH)ACRYLATE MONOMER AND ZINC SALT

Description

FIELD OF THE INVENTION

[0001] The present invention relates to a composition based on (meth)acrylate monomer and zinc salt.

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

[0003] 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.

[0004] 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 OO bond of the organic peroxide, for example, and initiates polymerization.

[0005] However, one of the problems with this technique is inhibition by oxygen. Indeed, the oxygen present in the air in its triplet state will interact with the radicals formed on the surface of the sample, thus preventing them from initiating polymerization. This inhibition is expressed mainly on the surface since the oxygen penetrates little or not at all in depth depending on the deposited weight. In addition, the polymerization reaction is often slow for surfaces exposed to atmospheric oxygen which, partially polymerized, often remain sticky or "tacky". US2014 / 235758A1 describes a crosslinkable two-component composition comprising a component A comprising, among others, a (meth)acrylate monomer, a tertiary amine as a reducing agent, zinc neodecanoate as a zinc salt, a core-shell type impact modifier and a component B comprising, among others, a benzoyl peroxide as an oxidizing agent and a plasticizer.

[0006] There is a need for new (meth)acrylic compositions capable of at least partially overcoming at least one of the aforementioned drawbacks.

[0007] More particularly, there is a need for new (meth)acrylic compositions making it possible to reduce inhibition due to oxygen in the air, and in particular to lead to non-sticky crosslinked surfaces (“tack-free”).

[0008] There is also a need for new compositions that allow open time control depending on the intended application. Bonding applications on large parts such as wind turbines require compositions with a long open time, while bonding small electronic parts may require very short open times.

[0009] The open time is in particular the maximum time between the application of the adhesive composition on a substrate, and the display of the two substrates to be bonded, without degradation of the adhesive power. DESCRIPTION OF THE INVENTION A. Composition

[0010] The present invention relates to a crosslinkable two-component composition comprising: a component A comprising: ∘ a (meth)acrylate monomer; ∘ a reducing agent; ∘ a zinc salt chosen from zinc alkane sulfonates, zinc acetate, and mixtures thereof; a component B comprising an oxidizing agent. (Meth)acrylate monomer

[0011] (Meth)acrylate monomers may comprise one (monofunctional) or several (meth)acrylate functions (polyfunctional).

[0012] The (meth)acrylate monomers can be chosen from the group consisting of: compounds having the following formula (A): CH 2 =C(R a< )-COOR b< (A) in which: R a< represents a hydrogen atom or an alkyl group comprising from 1 to 4 carbon atoms; R b< is chosen from the group consisting of alkyls, cycloalkyls, alkenyls, cycloalkenyls, alkylaryls, arylalkyls or aryls, said alkyls, cycloalkyls, alkenyls, cycloalkenyls, alkylaryls, arylalkyls or aryls possibly being optionally substituted and / or interrupted by at least one silane, a silicone, an oxygen, a halogen, a carbonyl, a hydroxyl, an ester, a urea, a urethane, a carbonate, an amine, an amide, a sulfur, a sulfonate, or a sulfone; polyethylene glycol di(meth)acrylates; polypropylene glycol di(meth)acrylates; tetrahydrofuran (meth)acrylates; hydroxyalkyl(meth)acrylates such as, for example, hydroxypropyl(meth)acrylate or hydroxyethyl(meth)acrylate;hexanediol di(meth)acrylate; trimethylol propane tri(meth)acrylate; diethylene glycol di(meth)acrylate; triethylene glycol di(meth)acrylate; tetraethylene glycol di(meth)acrylate; dipropylene glycol di(meth)acrylate; di-(pentamethylene glycol di(meth)acrylate; diglycerol tetra(meth)acrylate; tetramethylene di(meth)acrylate; ethylene di(meth)acrylate; bisphenol A mono- and di(meth)acrylates; bisphenol F mono- and di(meth)acrylates; and mixtures thereof. ;

[0013] According to one embodiment, the (meth)acrylate monomer is chosen from methyl (meth)acrylate, ethyl (meth)acrylate, 2-ethylhexyl (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, 3-vinylcyclohexyl (meth)acrylate, bornyl (meth)acrylate, 2,4,5-tri-t-butyl-3-vinylcyclohexyl (meth)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, and mixtures thereof.,

[0014] Preferably, the (meth)acrylate monomer is a methacrylate.

[0015] Preferably, the (meth)acrylate monomer is methyl methacrylate.

[0016] Component A may comprise a total content of (meth)acrylate monomer(s) ranging from 20% to 80%, preferably from 30% to 70%, advantageously from 40% to 60% by weight relative to the total weight of said component A. Reducing agent

[0017] The reducing agent may be selected from tertiary amines, sodium metabisulfite, sodium bisulfite, transition metals, azo compounds, alpha-aminosulfones, and mixtures thereof.

[0018] Among the azo compounds, we can cite for example azoisobutyric acid.

[0019] Among the alpha-sulfones, we can for example cite bis(tolylsulfonmethyl)benzylamine.

[0020] Tertiary amines include, for example, diisopropanol-p-toluidine (DIIPT); dimethyl-p-toluidine; dipropoxy-p-toluidine; dimethylaniline; N,N-dimethylaminomethylphenol; N,N-diisopropanol-p-chloroaniline; N,N-diisopropanol-p-bromoaniline; N,N-diisopropanol-p-bromo-m-methylaniline; N,N-dimethyl-p-chloroaniline; N,N-dimethyl-p-bromoaniline; N,N-diethyl-p-chloroaniline; N,N-diethyl-p-bromoaniline; amines having the following formulae (I) or (II); and mixtures thereof: in which:m and n are, independently of each other, an integer ranging from 1 to 150, preferably from 1 to 100, preferentially from 1 to 72, advantageously from 1 to 36, even more advantageously from 1 to 18; r is an integer ranging from 1 to 200, preferably from 1 to 104, preferentially from 1 to 72, advantageously from 1 to 36; R 1 represents a radical chosen from the group consisting of an alkyl, linear or branched, saturated or unsaturated, comprising from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms; of a (hetero)aryl comprising from 6 to 12 carbon atoms; of a cycloalkyl comprising from 3 to 12 carbon atoms; v represents an integer ranging from 0 to 5; R 2 and R 3 represent, independently of one another, a halogen atom, a hydrogen atom or a linear or branched alkyl group comprising from 1 to 12 carbon atoms, said alkyl group being optionally interrupted by at least one oxygen atom;R 4 represents a hydrogen atom, an arylalkyl group, or a linear or branched alkyl group comprising from 1 to 20 carbon atoms, preferably an alkyl group comprising from 1 to 12 carbon atoms, advantageously from 1 to 6 carbon atoms; provided that m + n > 2, preferably n + m ≥ 2.5. ;

[0021] In the above-mentioned formula (I), v is preferably 1, and R 1< is preferably in the para position.

[0022] The amines of formula (I) are preferably chosen from those in which: R 1< represents a linear or branched, saturated or unsaturated alkyl, comprising from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, preferably R 1< represents methyl; m and n represent, independently of each other, an integer ranging from 1 to 18, preferably from 1 to 9, advantageously from 1 to 5; R 2< and R 3< represent, independently of each other, a hydrogen atom or a linear or branched alkyl group, comprising from 1 to 12 carbon atoms, said alkyl group being optionally interrupted by at least one oxygen atom, preferably R 2< and R 3< each represents a hydrogen atom; with m + n > 2, preferably n + m ≥ 2.5.

[0023] Preferably, the amines of formula (I) are those in which: R 1< represents a linear or branched alkyl, comprising from 1 to 5 carbon atoms, preferably R 1< represents methyl; m and n represent, independently of one another, an integer ranging from 1 to 18, preferably from 1 to 9, advantageously from 1 to 5; R 2< and R 3< represent a hydrogen atom; with m + n > 2, preferably n + m ≥ 2.5.

[0024] Among the amines of formula (I), we can for example cite “BISOMER ®< PTE” (CAS number: 878391-30-1) marketed by GEO SPECIALITY CHEMICALS, “Accelerator PT25E” (CAS number: 878391-30-1) marketed by LANXESS, N,N-Bis(2-hydroxypropyl)-p-aniline (CAS number: 3077-13-2) available from BIOSYNTH, N,N-Bis(2-hydroxypropyl)-p-toluidine (CAS number: 38668-48-3) marketed by BASF, “ETHOX ANA-10” (CAS number: 36356-83-9) available from ETHOX CHEMICAL.

[0025] In the above-mentioned formula (II), v is preferably 1, and R 1< is preferably in the para position.

[0026] The amines of formula (II) are preferably chosen from those in which: R 1< represents a linear or branched, saturated or unsaturated alkyl, comprising from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, preferably R 1< represents methyl; r represents an integer ranging from 1 to 36, preferably from 1 to 18, advantageously from 1 to 10; R 3< represents a halogen atom, a hydrogen atom or a linear or branched alkyl group, comprising from 1 to 12 carbon atoms, said alkyl group being optionally interrupted by at least one oxygen atom, R 4< represents a hydrogen atom, an arylalkyl group, or a linear or branched alkyl group, comprising from 1 to 20 carbon atoms, preferably from 1 to 6 carbon atoms.

[0027] Among the amines of formula (II), we can cite for example N-(2-hydroxyethyl)-N-methyl aniline (CAS number: 93-90-3) available from SIGMA-ALDRICH and N-(2-hydroxyethyl)-N-methyl-p-toluidine (MHPT, CAS number: 2842-44-6) available from PARCHEM.

[0028] Preferably, component A comprises at least one tertiary amine as reducing agent, and even more preferably an amine of formula (I) mentioned above.

[0029] Component A may comprise a total content of reducing agent(s) ranging from 0.1% to 5%, preferably from 0.5% to 3%, by weight relative to the total weight of said component A. Oxidizing agent

[0030] The oxidizing agent may be chosen from peroxides, organic salts of transition metals, compounds containing labile chlorine, and mixtures thereof.

[0031] The peroxide may be chosen from organic peroxides, inorganic peroxides, and mixtures thereof.

[0032] Inorganic peroxides include peroxydisulfuric acid and their salts, such as ammonium peroxodisulfate, sodium peroxodisulfate, and potassium peroxodisulfate.

[0033] Organic peroxides include cumene hydroperoxide, para-menthane hydroperoxide, tert-butyl peroxyisobutyrate, tert-butyl peroxybenzoate, tert-butyl peroxyneodecanoate, tert-amyl peroxypivalate, acetyl peroxide, benzoyl peroxide, dibenzoyl peroxide, 1,3-bis-(t-butylperoxyisopropyl)benzene, diacetyl peroxide, t-butylcumyl peroxide, tert-butyl peroxyacetate, cumyl peroxide, 2,5-dimethyl-2,5-di-t-butylperoxyhexane, 2,5-dimethyl-2,5-di-t-butyl-peroxyhex-3-yne, 4-methyl-2,2-di-t-butylperoxypentane, and their mixtures.

[0034] Preferably, component B comprises benzoyl peroxide as an oxidizing agent.

[0035] Component B may comprise a total content of oxidizing agent(s) ranging from 1% to 50%, preferably from 10% to 40% by weight relative to the total weight of said component B.

[0036] The composition according to the invention may typically comprise a redox system, a reducing agent being included in component A and an oxidizing agent being included in component B. Examples of the following combinations may be cited: persulfates (oxidant) / (sodium metabisulfite and / or sodium bisulfite) (reducers); organic peroxides (oxidant) / tertiary amines (reducer); organic hydroperoxides (oxidant) / transition metals (reducer). Zinc salts

[0037] Component A comprises a zinc salt selected from zinc alkane sulfonates, zinc acetate, and mixtures thereof.

[0038] Zinc salt also covers hydrated zinc salts.

[0039] In the context of the invention, and unless otherwise stated, alkane sulfonates are understood to mean aliphatic sulfonates.

[0040] Zinc alkane sulfonates may have one of the following formulae (III) or (IV): (R'-SO 3 ) 2 -< , Zn 2+< (III) (OH-R"-SO 3 ) 2 -< , Zn 2+< (IV) in which R' represents a linear or branched hydrocarbon radical comprising from 1 to 18 carbon atoms, and R" represents a linear or branched hydrocarbon radical comprising from 2 to 18 carbon atoms.

[0041] Preferably, in formula (IV), R" represents a linear or branched alkyl comprising from 2 to 18 carbon atoms, preferably from 2 to 6 carbon atoms, and even more preferably from 2 to 4 carbon atoms.

[0042] According to a preferred embodiment, in the above-mentioned formula (III), R' represents a branched or linear alkyl comprising from 1 to 18 carbon atoms, preferably from 1 to 6 carbon atoms, and even more preferably one carbon atom.

[0043] Among the alkane sulfonates of formula (III), we can for example cite zinc methane sulfonate (R' = Methyl), zinc dodecane sulfonate (R' = C12), or zinc octadecane sulfonate (R' = C18), the zinc alkane sulfonate being preferentially zinc methane sulfonate.

[0044] Zinc alkane sulfonates are typically commercially available.

[0045] According to a preferred embodiment, component A comprises a zinc salt being zinc acetate dihydrate.

[0046] Component A may comprise a total content of zinc salt(s) as defined above ranging from 0.1% to 10%, preferably from 0.5% to 5%, and even more preferably from 0.5% to 2% by weight relative to the total weight of said component A. Additional ingredients

[0047] The two-component composition may include at least one additional ingredient selected from the group consisting of catalysts, fillers, antioxidants, light stabilizers / UV absorbers, metal deactivators, antistatics, antifogging agents, foaming agents, biocides, plasticizers, lubricants, emulsifiers, colorants, pigments, rheological agents, impact modifiers, adhesion promoters, optical brighteners, flame retardants, anti-bleeding agents, nucleating agents, solvents, and mixtures thereof.

[0048] These ingredients may be present in component A and / or component B of the composition according to the invention.

[0049] 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.

[0050] Preferably, we use: diisodecyl phthalate, such as for example marketed under the name PALATINOL ™< DIDP by BASF, an ester of alkylsulfonic acid and phenol, such as for example marketed under the name MESAMOLL ®< by LANXESS, diisononyl-1,2-cyclohexanedicarboxylate, such as for example marketed under the name HEXAMOLL DINCH ®< by BASF, pentaerythritol tetravalerate, such as for example marketed under the name PEVALEN ™< by PERSTORP, epoxidized soybean oil such as for example marketed under the name VIKOFLEX ®< 7170 by ARKEMA.

[0051] As an example of rheology agent(s) (thixotropic) that can be used, mention may be made of any rheology agent usually used in the field of adhesive compositions.

[0052] 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 the company 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 marketed by Arkema.

[0053] The composition according to the invention may further comprise at least one organic and / or mineral filler.

[0054] The mineral filler(s) that can be used is (are) advantageously chosen so as to improve the mechanical performance of the composition according to the invention in the crosslinked state.

[0055] As an example of the mineral filler(s) that can be used, any mineral filler(s) 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.

[0056] Preferably, the filler(s) is(are) chosen from the group consisting of clay, quartz, carbonate fillers, kaolin, gypsum, clays, and mixtures thereof, preferably the filler(s) is(are) chosen from carbonate fillers, such as alkali or alkaline-earth metal carbonates, and more preferably calcium carbonate or chalk.

[0057] 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.

[0058] Hollow mineral microspheres such as hollow glass microspheres, and more particularly those made of sodium and calcium borosilicate or aluminosilicate, can also be used.

[0059] 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, or phosphate ester-based adhesion promoters such as, for example, 2-hydroxyethyl methacrylate phosphate ester, 2-methacryloyloxyethyl phosphate, bis-(2-methacryloyloxyethyl phosphate), 2-acryloyloxyethyl phosphate, bis-(2-acryloyloxyethyl phosphate), methyl-(2-methacryloyloxyethyl phosphate), ethyl-(2-methacryloyloxyethyl phosphate), a mixture of mono- and di-phosphate esters of 2-hydroxyethyl methacrylate. The composition may comprise from 0% to 5% by total weight of adhesion promoter(s).

[0060] When a solvent, in particular a volatile solvent, is present in the composition, its content is preferably less than or equal to 5% by weight, more preferably less than or equal to 3% by weight, relative to the total weight of the composition.

[0061] Preferably, the content of solvent(s) in the composition is between 0% and 5% by weight.

[0062] 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 it is 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.

[0063] Pigments can be organic or inorganic pigments.

[0064] For example, the pigment is TiO 2 , in particular KRONOS ®< 2059 marketed by the KRONOS company.

[0065] 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. Examples include IRGANOX ®< 1010, IRGANOX ®< B561, IRGANOX ®< 245, IRGAFOS ®< 168, TINUVIN ®< 328 or TINUVIN ™< 770 marketed by BASF.

[0066] The composition may include at least one acrylic block copolymer. Acrylic block copolymers are typically impact modifiers.

[0067] Acrylic block copolymers may be copolymers comprising: from 1% to 99% of at least one rigid block (A) whose glass transition temperature is at least 20°C higher than room temperature; from 1 to 99% by weight of at least one flexible block (B) whose glass transition temperature is at least 10°C lower than room temperature.

[0068] The copolymers can in particular be rigid block / soft block / rigid block triblocks, in which: at least one rigid block (A) of the copolymer is advantageously made up of monomer units derived from at least one methacrylate of formula CH 2 =C(CH 3 )-COOR i where R i is a linear or branched C1-C3 alkyl group, a branched C4 group, a C3-C8 cycloalkyl group, a C6-C20 aryl group, a C7-C30 arylalkyl group containing a C1-C4 alkyl group, a heterocyclic group or a heterocyclylalkyl group containing a C1-C4 alkyl group; and the flexible block (B) advantageously contains: (i) monomeric units derived from at least one alkyl acrylate of formula CH 2 =CH-COOR j where R j is a linear or branched C1-C12 alkyl group, and / or (ii) monomeric units derived from at least one methacrylate of formula CH 2 =C (CH 3 )-COOR k where R k is a linear C4-C12 alkyl group or a branched C5-C12 alkyl group.

[0069] The rigid block (A) preferably comprises monomeric units derived from methyl methacrylate monomers.

[0070] The rigid block (A) may further comprise at least one dialkylacrylamide monomer whose linear or branched alkyl groups comprise from 1 to 10 carbon atoms, such as N,N-dimethylacrylamide.

[0071] The flexible block (B) preferably comprises monomeric units derived from at least one monomer chosen from butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, 2-ethylhexyl methacrylate, n-octyl acrylate and mixtures thereof.

[0072] Preferably, the copolymer is a polymethyl methacrylate / polyn-butyl acrylate / polymethyl methacrylate block copolymer.

[0073] Among the acrylic block copolymers, we can for example cite Nanostrength ®< marketed by Arkema (M52 comprising 52% by weight of n-butyl polyacrylate, or M75 comprising approximately 75% by weight of n-butyl polyacrylate or M65 comprising approximately 65% ​​by weight of n-butyl polyacrylate).

[0074] The composition may comprise an impact modifier having a core-shell type structure, typically known as a "core-shell impact modifier". Impact modifiers are well known to those skilled in the art, and include in particular impact modifiers having a core-shell type structure.

[0075] The impact modifier having a core-shell structure may be in the form of spherical particles. The weight-average particle size (diameter) may range from 40 nm to 900 nm, preferably from 80 to 500 nm. The particle size may be measured with a Zetasizer (Malvern).

[0076] The impact modifier having a core-shell type structure can be obtained by any method known to those skilled in the art, for example by a multi-step method as described in FR 3 052 169 or in EP 2 465 884. In particular, the polymer is prepared by emulsion polymerization.

[0077] The core of the impact modifier may comprise a polymer L1 selected from isoprene homopolymers, butadiene homopolymers, isoprene-butadiene copolymers, isoprene copolymers with a vinyl monomer, butadiene copolymers with a vinyl monomer. The vinyl monomer may be selected from styrene, alkylstyrene, acrylonitrile, alkyl (meth)acrylates, butadiene or isoprene.

[0078] The shell may comprise a polymer L2 obtained from (meth)acrylic monomers such as, for example, those chosen from C1-C12 alkyl (meth)acrylates. In particular, the shell comprises a polymer L2 obtained from C1-C4 alkyl methacrylate monomers and / or C1-C8 alkyl acrylate monomers.

[0079] Preferably, the bark comprises a polymer L2 obtained from methyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and mixtures thereof.

[0080] According to one embodiment, the impact modifier having a core-shell type structure comprises: a core comprising a polymer L1 being a butadiene-styrene copolymer; a bark comprising a polymer L2 being a polymethyl methacrylate (PMMA).

[0081] Impact modifiers with a core-shell structure may be commercially available. Examples include Clearstrength ®< (e.g., Clearstrength ®< XT100) or Durastrength ®< marketed by Arkema. Other products include Paraloid (Paraloid 2650A, Paraloid 2691A) marketed by Dow Corning.

[0082] The total content of impact modifier(s) in component A may range from 2% to 30% by weight, preferably from 5% to 20% by weight relative to the total weight of component A.

[0083] The composition may comprise at least one urethane-acrylate having a number-average molecular mass greater than or equal to 2,000 g / mol, preferably greater than or equal to 4,000 g / mol.

[0084] Urethane-acrylates can be obtained by reaction between a polyol and a polyisocyanate, followed by functionalization with, for example, hydroxymethyl methacrylate.

[0085] There are many commercially available urethane-acrylates.

[0086] According to one embodiment, the volume ratio of component A / component B in the composition of the invention ranges from 100 / 5 to 1 / 1, preferably from 20 / 1 to 1 / 1, preferentially from 10 / 1 to 1 / 1.

[0087] According to a preferred embodiment, the above-mentioned composition comprises: a component A comprising: from 20% to 80% by weight of (meth)acrylate monomer(s); from 0.1% to 5% by weight of reducing agent(s); from 0.1% to 10% by weight of zinc salt(s) as defined above, chosen from zinc alkane sulfonates, zinc acetate, and mixtures thereof; from 2% to 30% by weight of core-shell type impact modifier(s); from 0% to 40% by weight of urethane-acrylate compound(s); relative to the total weight of said component A; a component B comprising: from 1% to 50% by weight of oxidizing agent(s); and from 20% to 80% by weight of plasticizer(s); relative to the total weight of said component B.

[0088] Preferably, the composition according to the invention is an adhesive composition. Ready-to-use kit

[0089] 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.

[0090] 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.

[0091] 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 and static mixers of a diameter adapted to the quantities used. Uses of the compositions

[0092] The present invention also relates to the use of a composition as defined above, as an adhesive, sealant or coating, preferably as an adhesive.

[0093] The invention also relates to the use of said composition for the repair and / or structural or semi-structural bonding of materials in the field of transport, automotive (car, bus or truck), electronics, assembly, wind power, marine, or construction.

[0094] The present invention also relates to a method of assembling two substrates by gluing, comprising: coating on at least one of the two substrates to be assembled a composition obtained by mixing components A and B as defined previously; then effectively bringing the two substrates into contact; crosslinking the composition.

[0095] 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.

[0096] 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.

[0097] The compositions according to the invention advantageously allow polymerization which takes place on the surface and in depth. In addition, the surface of the crosslinked compositions dries quickly and is not "tacky", which advantageously makes it possible to increase the productivity of industrial processes and the appearance of bonds by limiting the incorporation of dust.

[0098] The compositions according to the invention advantageously have, after crosslinking, good adhesive properties.

[0099] Furthermore, the use of zinc salt in the compositions according to the invention advantageously makes it possible to control the open time according to the intended application. For example, the use of zinc carboxylate according to the invention advantageously makes it possible to reduce the open time and therefore to accelerate the reaction.

[0100] 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.

[0101] 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%.

[0102] 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. EXAMPLES

[0103] The following ingredients were used: BISOMER ®< PTE (CAS Number: 103671-44-9) marketed by GEO Specialty Chemicals; methyl methacrylate (MMA) marketed by Aldrich; MBS CLEARSTRENGTH ®< XT100 marketed by ARKEMA is a core-shell impact modifier based on MMA-butadiene-styrene; CN ®< 981 marketed by SARTOMER is a urethane-acrylate with functionality 2 and Mw of 2000 g / mol; Zinc methane sulfonate (CAS 33684-80-9) marketed by ALDRICH; Valikat ®< ZN 1910 marketed by UMICORE is a zinc(ll) neodecanoate; Zinc acetate dihydrate (CAS 5970-45-6) marketed by ALDRICH; Methacrylic acid marketed by ALDRICH; SR9054 (CAS No.: 1628778-81-3) marketed by SARTOMER is a mixture of methacrylates comprising phosphonic acid functions; HDK ®< N20 marketed by WACKER is a fumed silica; TALCRON ®< CL40 marketed by MINERALS GIRONA is a magnesium hydrosilicate;PEROXAN ™< BP 50 marketed by PERGAN is a 50% benzoyl peroxide paste; CRAYVALLAC ®< SLT marketed by ARKEMA is a micronized amide wax used as a rheological agent; VIKOFLEX ®< 7170 marketed by ARKEMA is an epoxidized soybean oil used as a plasticizer. ; Example 1 : preparation of compositions

[0104] In a reactor maintained under constant stirring and under nitrogen, the ingredients constituting component A are added in the proportions indicated in the following table at a temperature of 23°C.

[0105] In a reactor maintained under constant stirring and under nitrogen, the different ingredients constituting component B are mixed in the proportions indicated in the following table at a temperature of 23°C. Compositions No. 1 to 3 Component A Component B ingredients % by weight (relative to the total weight of A) ingredients % by weight (relative to the total weight of B) MMA 44,33 PEROXAN ™< BPO 35 Clearstength ®< XT100 10 VIKOFLEX ®< 7170 62 CN981 27,8 CRAYVALLAC ®< SLT 10 methacrylic acid 1,11 SR9054 2,22 HDK ®< N20 5,55 Crayvallac ®< SLT 3,55 Talkron ®< CL40 3,22 Bisomer ®< PTE 1,11 Zinc salt* 1,11 100% 100%

[0106] Three different compositions were prepared with different zinc salts: Zinc salt Zinc acetate dihydrate Composition No. 1 VALIKAT ®< ZN 1910 Composition No. 2 Zinc methane sulfonate Composition No. 3

[0107] The mixture is carried out at a temperature of approximately 23°C, in a volume ratio of 10:1 (component A: component B) with a static mixer. Example 2 : Results Temperature test and polymerization time after mixing components A and B

[0108] There figure 1 represents the temperature T(in °C) = f(time in minutes) which was obtained with compositions n°1, n°2 and n°3 (respectively curves 1, 2 and 3). The test is carried out using a sacrificial thermocouple in a 30 ml mixing volume. This test makes it possible to determine the exothermicity of the reaction and the lag time, i.e. the time it takes for the sample to start polymerizing. This time is the gel time.

[0109] There figure 1shows that composition No. 1 with zinc acetate dihydrate leads to an exotherm (temperature peak) in a short time of around 30 minutes, whereas it is more than 90 minutes with composition No. 3. Thus, for the same composition, the open time can be varied according to the desired application, by modifying the nature of the zinc salt. Composition No. 3, with a long open time, could be used advantageously in the wind energy sector where large blades require an open time of at least one to two hours to bond such parts. Inhibition result

[0110] The inhibition of the glue is observed by contact with the surface of the two-component mixture, which must be dry and without stickiness, using a tongue depressor or a paper strip. In terms of inhibition, the following table groups the results with compositions No. 1, No. 2 and No. 3: Composition No. results 1 ++ 2 + 3 +

Claims

1. Two-component crosslinkable composition comprising: - a component A comprising: ∘ a (meth)acrylate monomer; ∘ a reducing agent; ∘ a zinc salt chosen from zinc alkanesulfonates, zinc acetate, and mixtures thereof; - a component B comprising an oxidizing agent.

2. Composition according to Claim 1, characterized in that the reducing agent is chosen from tertiary amines, sodium metabisulfite, sodium bisulfite, transition metals, azo compounds, alpha-aminosulfones, and mixtures thereof.

3. Composition according to either one of Claims 1 and 2, characterized in that the reducing agent is a tertiary amine, and even more preferentially an amine having the formula (I) or (II) below: wherein: - m and n are, independently of one another, an integer ranging from 1 to 150, preferably from 1 to 100, preferentially from 1 to 72, advantageously from 1 to 36, more advantageously still from 1 to 18; - r is an integer ranging from 1 to 200, preferably from 1 to 104, preferentially from 1 to 72, advantageously from 1 to 36; - R1 represents a radical chosen from the group consisting of a saturated or unsaturated and linear or branched alkyl comprising from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms; of a (hetero)aryl comprising from 6 to 12 carbon atoms; of a cycloalkyl comprising from 3 to 12 carbon atoms; - v represents an integer ranging from 0 to 5; - R2 and R3 represent, independently of one another, a halogen atom, a hydrogen atom or a linear or branched alkyl group comprising from 1 to 12 carbon atoms, said alkyl group being optionally interrupted by at least one oxygen atom; - R4 represents a hydrogen atom, an arylalkyl group or a linear or branched alkyl group comprising from 1 to 20 carbon atoms, preferably an alkyl group comprising from 1 to 12 carbon atoms, advantageously from 1 to 6 carbon atoms; - on the condition that m + n > 2, preferably n + m ≥ 2.5.

4. Composition according to any one of Claims 1 to 3, characterized in that component A comprises a total content of reducing agent(s) ranging from 0.1% to 5%, preferably from 0.5% to 3%, by weight relative to the total weight of said component A.

5. Composition according to any one of Claims 1 to 4, characterized in that the zinc alkanesulfonates have one of the formulae (III) or (IV) below:         (R'-SO3)2-, Zn2+     (III)         (OH-R"-SO3)2-, Zn2+     (IV) wherein R' represents a linear or branched hydrocarbon radical comprising from 1 to 18 carbon atoms, and R" represents a linear or branched hydrocarbon radical comprising from 2 to 18 carbon atoms.

6. Composition according to any one of Claims 1 and 5, characterized in that the total content of zinc salt(s) in component A ranges from 0.1% to 10%, preferably from 0.5% to 5%, and more preferentially still from 0.5% to 2% by weight relative to the total weight of said component A.

7. Composition according to any one of Claims 1 to 6, characterized in that the (meth)acrylate monomer is chosen from the group consisting of: - compounds having formula (A) below:         CH2=C(Ra)-COORb     (A) wherein: - Ra represents a hydrogen atom or an alkyl group comprising from 1 to 4 carbon atoms; - Rb is chosen from the group consisting of alkyls, cycloalkyls, alkenyls, cycloalkenyls, alkylaryls, arylalkyls and aryls, it being possible for said alkyls, cycloalkyls, alkenyls, cycloalkenyls, alkylaryls, arylalkyls or aryls to be optionally substituted and / or interrupted by at least one silane, one silicone, one oxygen, one halogen, one carbonyl, one hydroxyl, one ester, one urea, one urethane, one carbonate, one amine, one amide, one sulfur, one sulfonate or one sulfone; - polyethylene glycol di(meth)acrylates; - polypropylene glycol di(meth)acrylates; - tetrahydrofuran (meth)acrylates; - hydroxyalkyl (meth)acrylates such as, for example, hydroxypropyl (meth)acrylate or hydroxyethyl (meth)acrylate; - hexanediol di(meth)acrylate; - trimethylolpropane tri(meth)acrylate; - diethylene glycol di(meth)acrylate; - triethylene glycol di(meth)acrylate; - tetraethylene glycol di(meth)acrylate; - dipropylene glycol di(meth)acrylate; - di(pentamethylene glycol) di(meth)acrylate; - diglyceryl tetra(meth)acrylate; - tetramethylene di(meth)acrylate; - ethylene di(meth)acrylate; - bisphenol A mono- and di(meth)acrylates; - bisphenol F mono- and di(meth)acrylates; and - mixtures thereof.

8. Composition according to any one of Claims 1 to 7, characterized in that the (meth)acrylate monomer is chosen from methyl (meth)acrylate, ethyl (meth)acrylate, 2-ethylhexyl (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, 3-vinylcyclohexyl (meth)acrylate, bornyl (metha)crylate, 2,4,5-tri-t-butyl-3-vinylcyclohexyl (meth)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, and mixtures thereof.

9. Composition according to any one of Claims 1 to 8, characterized in that component A comprises a total content of (meth)acrylate monomer(s) ranging from 20% to 80%, preferably from 30% to 70%, advantageously from 40% to 60% by weight relative to the total weight of said component A.

10. Composition according to any one of Claims 1 to 9, characterized in that it comprises at least one additional ingredient chosen from the group consisting of catalysts, fillers, antioxidants, light stabilizers / UV absorbers, metal deactivators, antistatic agents, antifogging agents, foaming agents, biocides, plasticizers, lubricants, emulsifiers, dyes, pigments, rheological agents, impact modifiers, adhesion promoters, optical brighteners, flame retardants, antisweating agents, nucleating agents, solvents, and mixtures thereof.

11. Composition according to any one of Claims 1 to 10, characterized in that it comprises: - a component A comprising: - from 20% to 80% by weight of (meth)acrylate monomer(s); - from 0.1% to 5% by weight of reducing agent(s); - from 0.1% to 10% by weight of zinc salt(s) as defined in Claim 1; - from 2% to 30% by weight of core-shell impact modifier(s); - from 0% to 40% by weight of urethane-acrylate compound(s); relative to the total weight of said component A; - a component B comprising: - from 1% to 50% by weight of oxidizing agent(s); and - from 20% to 80% by weight of plasticizer(s); relative to the total weight of said component B.

12. Composition according to any one of Claims 1 to 11, characterized in that component A / component B volume ratio ranges from 100 / 5 to 1 / 1, preferably from 20 / 1 to 1 / 1, preferentially from 10 / 1 to 1 / 1.

13. Use of a composition as defined in one of Claims 1 to 12, as an adhesive, mastic or coating, preferably as an adhesive.

14. Process for assembling two substrates by adhesive bonding, comprising: - coating at least one of the two substrates to be assembled with a composition obtained by mixing components A and B as defined in any one of Claims 1 to 12; and then - effectively bringing the two substrates into contact; - crosslinking the composition.