Composition based on (meth)acrylate monomers

Abstract

Composition based on (meth)acrylate monomers. The present invention relates to a crosslinkable two-component composition comprising: - a component A comprising: - an iodonium salt having one of the formulas (IA), (IB), or (IC); - at least one (meth)acrylate monomer M1 having one of the formulas (II), (III), or (IV); - an organic or mineral acid having a pKa or pKa1 ranging from 0.3 to 5 measured in water at 25°C; - a copper salt or a copper complex; - a component B comprising at least one dihydropyridine compound having one of the formulas (VI) to (X), said composition not comprising any peroxide. FIGURE: NONE

Description

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

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

[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, assembly, electronics or construction. TECHNOLOGICAL BACKGROUND

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

[0004] The majority of acrylic systems are two-component systems. The first component traditionally contains the reducing agent and the reactive monomers, and the second component contains the oxidizing agent. Once the two components are mixed, the reducing agent induces the cleavage of the 0-0 bond of the organic peroxide, for example, and initiates the polymerization.

[0005] Typically, (meth)acrylic compositions comprise a peroxide (oxidant) / tertiary amine (reducer) type redox system. However, these systems may have storage stability problems in the presence of (meth)acrylate monomer.

[0006] There is a need for new (meth)acrylic compositions allowing a good compromise between reactivity and storage stability.

[0007] Furthermore, there is also a need for new (meth)acrylic compositions having good adhesive properties. DESCRIPTION OF THE INVENTION A. Composition

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

[0009] - a component A comprising:

[0010] - an iodonium salt having one of the following formulas (LA), (LB) or (LC):

[0011] [Chem.l]

[0012] in which: - R1 and R2 each represent, independently of one another, a hydrogen atom, an alkyl radical, an alkenyl radical, a cycloalkyl radical, a cycloalkenyl radical, an aryl radical, a chlorine atom, a bromine atom, an iodine atom, a carboxylic radical, or a -NO2 radical; - X represents a monovalent anion; - W represents O or S;

[0013] - at least one (meth)acrylate monomer Ml having one of the formulas (II), (III) or (IV) following:

[0014] [Chem.2] (IV)

[0015] in which:

[0016] - R3 represents H or a methyl;

[0017] - R4 represents H, methyl or ethyl;

[0018] - p represents 0 or 1; and

[0019] - Z represents H, O, S, an alkyl group, a benzyl group, an aryl group, or a alkoxy group;

[0020] - Y represents O, S, NH or CH2;

[0021] - a single bond or a double bond,

[0022] provided that when Z represents O, then the bond ^^is a double bond;

[0023] - an organic or mineral acid having a pKa or pKal ranging from 0.3 to 5.0 measured in water at 25°C;

[0024] - optionally a copper salt of formula (VI) or a copper complex of formula (V-2):

[0025] [Chem.3]

[0026] in which:

[0027] - R and R” each represents, independently of one another, an alkyl radical, a cycloalkyl radical, an aryl radical, a heteroaryl radical,

[0028] - R' represents a hydrogen atom, an alkyl radical, a cycloalkyl radical, a aryl radical, a heteroaryl radical,

[0029] or R and R' (or R' and R”) can 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);

[0030] - a component B comprising at least one dihydropyridine compound having one of the following formulas (VI) to (X):

[0031] [Chem.4] (=X) (X)

[0032] in which: - each of R5 to R11 represents, independently of one another, a hydrogen, an alkyl, an alkenyl, an alkynyl, a cycloalkyl, a heterocycloalkyl, a heteroaryl, an aryl, an alkylaryl, an arylalkyl, a radical -C00Ra;

[0033] said alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, heteroaryl, aryl, alkylaryl, arylalkyl groups being optionally substituted;

[0034] and Ra representing an alkyl or aryl radical;

[0035] or two radicals from R5 to R11 together form a mono- or polycyclic ring, optionally substituted,

[0036] said crosslinkable two-component composition not comprising peroxide.

[0037] In the context of the invention, the term "alkyl" means a linear or branched radical preferably comprising from 1 to 20 carbon atoms. Examples that may be mentioned are methyl, ethyl, propyl.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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, mention may for example be made of benzyl.

[0042] 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.

[0043] 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.

[0044] 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 norbodyl groups.

[0045] 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.

[0046] 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 possibly being two by two fused or bridged.

[0047] In the context of the invention, the term "alkoxy" means an -O-alkyl radical. Component A Iodonium salt of formula (IA), (IB) or (IC)

[0048] Component A comprises an iodonium salt having one of the formulas (LA), (LB) or (LC) as defined above.

[0049] Preferably, in the abovementioned formulas (LA), (LB) and (LC), R1 and R2 each represent, independently of one another, an alkyl radical or a hydrogen atom.

[0050] In the above-mentioned formulas (LA), (LB) and (LC), X may represent F, Cf, Br, I, NO3, HSO4, H2PO4, HCOO, CH3COO, BF4, AsF6, PF6, CH3-Ph-SO3, (F5Ph)4B or SbF6. Preferably, in the above-mentioned formulas (LA), (LB) and (LC), X represents BF4, PF6, CH3-Ph-SO3, (F5Ph)4B or SbF6. Even more preferably, X represents the anion (F5Ph)4B of the following formula:

[0051] [Chem. 5] — FF

[0052]

[0053] Among the iodonium salts of formula (IB), we can for example cite: [Chem. 6]

[0054]

[0055] Among the iodonium salts of formula (IC), we can for example cite: [Chem. 7]

[0056]

[0057]

[0058] Examples of iodonium salts of formula (IA) include diphenyl iodonium hexafluorophosphate, diphenyl iodonium fluoroborate, diphenyl iodonium 2-carboxylate, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, 3,3'-dimethyl diphenyl iodonium hexafluorophosphate, and (4-Isopropylphenyl)(4-methylphenyl)iodonium tetrakis(pentafluorophenyl)borate. Preferably, the iodonium salt is a salt of formula (IA). Even more preferably, the iodonium salt is (4-Isopropylphenyl)(4-methylphenyl)iodonium tetrakis(pentafluorophenyl)borate having the following formula: [Chem. 8]

[0059] Iodonium salts of formula (LA) can be prepared as described in US 4,151,175 or US 4,238,394. Iodonium salts of formula (LB) can be prepared as described in Journal of Fluorine Chemistry (2009), 130(5), 501-504. Iodonium salts of formula (LC) can be prepared as described in Journal of Heterocyclic Chemistry (1977), 14(2), 281-8.

[0060] The total content of iodonium salt of formula (IA), (IB) or (IC) may range from 0.05% to 5.0% by weight, preferably from 0.1% to 3.0% by weight, even more preferably from 0.1% to 1.5% by weight relative to the total weight of the crosslinkable two-component composition. (Meth)acrylate monomer Ml

[0061] Component A according to the invention comprises at least one (meth)acrylate monomer M1 having one of the following formulas (II), (III) or (IV):

[0062] [Chem.9]

[0063] in which:

[0064] - R3 represents H or methyl;

[0065] - R4 represents H, methyl or ethyl;

[0066] - p represents 0 or 1; and

[0067] - Z represents H, O, S, an alkyl group, a benzyl group, an aryl group, or a alkoxy group;

[0068] - Y represents O, S, NH or CH2;

[0069] - ^ ..-ycst a single bond or a double bond,

[0070] provided that when Z represents O, then the bond ^ <est une liaison double.

[0071] The (meth)acrylate monomer Ml can be chosen from the following monomers:

[0072] [Chem. 10]

[0073] The monomer M1 is preferably chosen from the monomers of formula (II) or (III). It is even more preferably one of the following compounds or their mixtures:

[0074] [Chem. 11] (mF) (mA)

[0075] The total content of (meth)acrylate monomer(s) M1 in component A may be greater than or equal to 20% by weight relative to the total weight of said component A.

[0076] The content of (meth)acrylate monomer(s) M1 in the crosslinkable two-component composition according to the invention may range from 20% to 99% by weight, preferably from 50% to 99% by weight, even more preferably from 75% to 99% by weight relative to the total weight of said crosslinkable two-component composition. Organic or mineral acid

[0077] Component A comprises an organic or mineral acid having a pKa or pKal ranging from 0.3 to 5 measured in water at 25°C.

[0078] The pKa (or acidity constant) is defined by pKa = -logi0 Ka, where Ka is the acid dissociation constant which is measured in a standard manner at 25°C. The standard measurement method recommended for pKa is in particular potentiometry, and more precisely pH-metry, as described for example in engineering techniques (ref. K695 vl). This method is the most used for determining pKa.

[0079] The pkal is defined by pKal = -logi0 Kal, where Kal is the acid dissociation constant of the first strongest acidity of the polyacids. Ka2 is the acid dissociation constant of the second acidity of polyacids (if any) and Ka3 is the acid dissociation constant of the third weakest acidity of polyacids (if any). To each of the successive acidities of a polyacid pKal, pKa2 or pKa3 correspond in particular decreasing values ​​of the acidity constants Kal, Ka2 and Ka3. The same standard measurement by potentiometry indicated previously is used to measure them.

[0080] Among the organic acids, we can for example cite carboxylic acids, phosphorus acids, and their mixtures.

[0081] Among the carboxylic acids, we can for example cite formic acid, acetic acid, monochloroacetic acid, monofluoroacetic acid, dichloroacetic acid, difluoroacetic acid, propionic acid, malic acid, fumaric acid, malonic acid, succinic acid, maleic acid, fumaric acid, citric acid, acrylic acid, methacrylic acid, cyanoacetic acid, salicylic acid, itaconic acid, benzoic acid, glycolic acid, thioglycolic acid, pyruvic acid, cinnamic acid, and mixtures thereof.

[0082] Among the mineral acids, we can for example cite phosphoric acid, phosphorous acid, methyl phosphonic acid, hypophosphorous acid, and their mixtures.

[0083] According to one embodiment, the acid has a pka or pkal ranging from 2 to 5, and in particular from 4 to 5.

[0084] According to a preferred embodiment, the acid having a pKa or pkal ranging from 0.3 to 5 is an organic acid chosen from carboxylic acids, and even more preferably chosen from acrylic acid, methacrylic acid, itaconic acid, salicylic acid, benzoic acid, monochloroacetic acid, monofluoroacetic acid, dichloroacetic acid, difluoroacetic acid and mixtures thereof. Even more preferably, it is dichloroacetic acid or difluoroacetic acid.

[0085] The total content of acid having a pka or pkal ranging from 0.3 to 5 may range from 0.1% to 20% by weight, preferably from 0.1% to 10% by weight, and even more preferably from 0.2% to 2% by weight relative to the total weight of the crosslinkable two-component composition.

[0086] Copper salt of formula (VI) or copper complex of formula (V-2)

[0087] Component A may comprise a copper salt of formula (VI) or a copper complex of formula (V-2):

[0088] [Chem. 12]

[0089] in which:

[0090] - R and R” each represents, independently of one another, an alkyl radical, a cycloalkyl radical, an aryl radical, a heteroaryl radical,

[0091] - R' represents a hydrogen atom, an alkyl radical, a cycloalkyl radical, a aryl radical, a heteroaryl radical,

[0092] or R and R' (or R' and R”) can 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).

[0093] Preferably, the salt of formula (VI) is that in which R represents an alkyl, even more preferably a methyl.

[0094] Preferably, the salt of formula (V-2) is that in which:

[0095] - R and R” each represents, independently of one another, an alkyl radical, a cycloalkyl radical, an aryl radical, a heteroaryl radical, preferably an alkyl radical;

[0096] - R' represents hydrogen.

[0097] The salt of formula (VI) is preferably copper acetate.

[0098] The copper complex of formula (V-2) is preferably copper acetylacetonate.

[0099] The total content of metal complex(es) of formula (V-2) may range from 0 ppm to 3,000 ppm by weight, preferably from 10 ppm to 2,000 ppm by weight, preferentially from 200 ppm to 2,000 ppm by weight, even more preferentially from 500 ppm to 1,500 ppm by weight relative to the total weight of the crosslinkable two-component composition. Component B Dihydropyridine compound of formulas (VI) to (X)

[0100] Component B comprises at least one dihydropyridine compound having one of formulas (VI) to (X) as defined above.

[0101] The dihydropyridine compound may be chosen from those of formulas (VI) to (X) in which: - R11 represents an aryl or heteroaryl, said aryl or heteroaryl being possibly substituted, and - from R5 to R10 represents, independently of each other, a hydrogen, an alkyl, an alkenyl, an alkynyl, a cycloalkyl, a heterocycloalkyl, a heteroaryl, an aryl, an alkylaryl, an arylalkyl,

[0102] R5 to R10 preferably representing, independently of one another, a hydrogen or an alkyl.

[0103] According to a preferred embodiment, the dihydropyridine compound has the formula (IX) or (X) as defined above.

[0104] The dihydropyridine compound may be chosen from the following compounds:

[0105] [Chem. 13] [Chem. 13]

[0106] According to a preferred embodiment, the dihydropyridine is the following compound:

[0107] [Chem. 14]

[0108] The dihydropyridines may be commercially available such as for example Vanax 808 HP cillercuakusé oar VANDERBILT CHEMICALS, or may be synthesized as described for example in WO 2006 / 086602.

[0109] The total content of dihydropyridine compound(s) having one of the formulas (VI) to (X) as defined above can range from 0.05% to 5.0% by weight, preferably from 0.1% to 3.0% by weight, and even more preferably from 0.1% to 1.5% by weight relative to the total weight of the crosslinkable two-component composition.

[0110] In the crosslinkable two-component composition according to the invention, the molar ratio of dihydropyridine compound(s) of formula (VI) to (X) / iodonium salt(s) of formula (IA) or (LB) or (LC) can range from 0.25 to 9, preferably from 0.5 to 6, and even more preferably from 0.9 to 3. Composition

[0111] The crosslinkable two-component composition according to the invention may comprise at least one other (meth)acrylate monomer M2 different from the monomer M1, and may be found in component A and / or component B.

[0112] The (meth)acrylate monomer(s) M2 may be chosen from the group consisting of:

[0113] - compounds having the following formula (XI): H2C=C(FH-COOFÜ3

[0114] in which: - R12 represents a hydrogen atom or a methyl group; - R13 is chosen from the group consisting of alkyls, cycloalkyls, alkenyls, cycloalkenyls, alkylaryls, arylalkyls or aryls, said alkyls, cycloalkyls, alkenyls, cycloalkenyls, alkylaryls, arylalkyls or aryls being able to be 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;

[0115] - polyethylene glycol di(meth)acrylates;

[0116] - tetrahydrofuran (meth)acrylates;

[0117] - hexanediol di(meth)acrylate;

[0118] - trimethylol propane tri(meth)acrylate;

[0119] - diethylene glycol di(meth)acrylate;

[0120] - triethylene glycol di(meth)acrylate;

[0121] - tetraethylene glycol di(meth)acrylate;

[0122] - dipropylene glycol di(meth)acrylate;

[0123] - di-(pentamethylene glycol di(meth)acrylate;

[0124] - diglycerol tetra(meth)acrylate;

[0125] - tetramethylene di(meth)acrylate;

[0126] - ethylene di(meth)acrylate;

[0127] - bisphenol A mono- and di(meth)acrylates;

[0128] - bisphenol F mono- and di(meth)acrylates; and

[0129] - of their mixtures.

[0130] The (meth)acrylate monomer M2 may in particular be chosen from methyl (meth)acrylate, ethyl (meth)acrylate, butyl (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.

[0131] The content of (meth)acrylate monomer(s) M2 in the two-component composition according to the invention may range from 0% to 69% by weight, preferably 0% to 49% by weight, and even more preferably from 0% to 24% by weight, relative to the total weight of said composition.

[0132] The content of the total sum of the (meth)acrylate monomer(s) M2 and the monomer(s) M1 in the two-component composition according to the invention may range from 30% to 99% by weight, preferably from 50% to 99% by weight, and even more preferably from 75% to 99% by weight, relative to the total weight of said composition.

[0133] According to one embodiment, the aforementioned two-component composition does not comprise hydroxyalkyl(meth)acrylate.

[0134] Component B as defined above may comprise at least one methacrylate monomer M1 as defined above.

[0135] The crosslinkable two-component composition according to the invention may comprise at least one additive chosen 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-seepage agents, nucleating agents, solvents, accelerators, and mixtures thereof.

[0136] These additives may be present in component A and / or component B of the composition according to the invention.

[0137] As an example of an accelerator, we can for example cite saccharin.

[0138] 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.

[0139] For example, we can use: - diisodecyl phthalate, such as that 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 the company LANXESS, - diisononyl-1,2-cyclohexanedicarboxylate, such as for example marketed under the name HEXAMOLL DINCH® by the company BASF, - pentaerythritol tetravalerate, such as for example marketed under the name PEVALEN™ by the company PERSTORP, - epoxidized soybean oil such as that marketed under the name VIKOFLEX® 7170 by ARKEMA.

[0140] As an example of rheology agent(s) (thixotropic) which can be used, mention may be made of any rheology agent usually used in the field of adhesive compositions.

[0141] 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 can be those described notably in the book “Polyurethane Sealants”, Robert M. Evans, ISBN 087762-998-6, - fumed silica, such as for example sold under the name HDK® N20 by WACKER; - urea derivatives resulting from the reaction of an aromatic diisocyanate monomer such as 4,4'-MDI with an aliphatic amine such as butylamine. The preparation of such urea derivatives is described in particular in application FR 1 591 172; - micronized amide waxes, such as CRAYVALLAC® SLT or CRAYVALLAC® SLA marketed by ARKEMA.

[0142] The composition according to the invention may further comprise at least one organic and / or mineral filler.

[0143] 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.

[0144] As an example of usable mineral filler(s), any mineral filler(s) usually used in the field of adhesive compositions may be used. These fillers are typically in the form of particles of various geometry. They may, for example, be spherical, fibrous, or have an irregular shape.

[0145] Preferably, the filler(s) is(are) chosen from the group consisting of clay, quartz, carbonated fillers, kaolin, gypsum, clays, and mixtures thereof, preferentially the filler(s) is(are) chosen from carbonated fillers, such as alkali or alkaline-earth metal carbonates, and more preferentially calcium carbonate or chalk.

[0146] These fillers may be untreated or treated, for example using an organic acid such as stearic acid, or a mixture of organic acids consisting mainly of stearic acid.

[0147] It is also possible to use hollow mineral microspheres such as hollow glass microspheres, and more particularly those made of sodium and calcium borosilicate or aluminosilicate.

[0148] 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 adhesion promoters based on phosphate ester 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.

[0149] 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.

[0150] The pigments can be organic or inorganic pigments.

[0151] For example, the pigment is TiO2, in particular KRONOS® 2059 marketed by the company KRONOS.

[0152] 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.

[0153] Examples include IRGANOX ® 1010, IRGANOX ® B561, IRGANOX ® 245, IRGAFOS ® 168, TINUVIN® 328 or TINUVIN™ 770 marketed by BASF.

[0154] 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. B. Ready-to-use kit

[0155] 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.

[0156] Indeed, the composition according to the invention can 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.

[0157] 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. C. Uses of the composition

[0158] 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.

[0159] 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), assembly, marine, electronics, or construction.

[0160] The present invention relates to a method of assembling two substrates by gluing, comprising: - coating on at least one of the two substrates to be assembled with a composition obtained by mixing components A and B as defined above; then - the effective contact of the two substrates; - crosslinking of the composition.

[0161] 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.

[0162] 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.

[0163] The crosslinking can be carried out under electromagnetic irradiation such as for example with a UV radiation source or with an LED.

[0164] 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.

[0165] The compositions according to the invention advantageously do not comprise peroxide. The compositions according to the invention advantageously lead to a good compromise between storage stability and high reactivity.

[0166] The compositions according to the invention advantageously have, after crosslinking, good adhesive properties.

[0167] . In addition, the surface of the crosslinked compositions advantageously dries quickly. and may not be “tacky”, which in particular helps to increase the productivity of industrial processes.

[0168] All the embodiments described above can be combined with each other. In particular, the various aforementioned constituents of the composition, and in particular the preferred modes of composition can be combined with each other.

[0169] 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%.

[0170] The invention is now described in the following exemplary embodiments which are given purely for illustrative purposes and cannot be interpreted to limit its scope. EXAMPLES

[0171] The following ingredients were used:

[0172] - SR® 531: cyclic trimethylolpropane formal acrylate (CAS: 66492-51-1) marketed by ARKEMA;

[0173] -SPEEDCURE® 939: (4-Isopropylphenyl)(4-methylphenyl)iodonium tetrakis(pentafluorophenyl)borate (CAS: 178233-72-2) marketed by LAMBSON;

[0174] - methyl methacrylate (MMA): marketed by ARKEMA;

[0175] - VANAX® 808 HP: 3,5-diethyl-l,2-dihydro-l-phenyl-2-propylpyridine (CAS: 34562-31-7) marketed by VERTELLUS SPECIALITIES;

[0176] - Cu(Acac)2: bis(acetylacetonato) of copper (II) (CAS: 13395-16-9) available from SIGMA-ALDRICH;

[0177] - Cu(OAc)2 (CAS: 142-71-2): copper (II) acetate available from Aldrich;

[0178] - Difluoroacetic acid (CAS: 381-73-7) available from SIGMA-ALDRICH. Example 1#: preparation of composition no. 1

[0179] In a mixer maintained under constant agitation and under nitrogen, the ingredients of component A are mixed in the proportions indicated in the following table at a temperature of 23°C.

[0180] In a mixer 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.

[0181] [Tables 1] Composition No. 1 Component A Component B ingredients % by weight (relative to the total weight of A) ingredients % by weight (relative to the total weight of B) Trimethylolpropane formal acrylate 97 Trimethylolpropane formal acrylate 99 (SR® 531) (SR® 531) Speedcure® 939 2 Vanax® 808 HP 1 Difluoroacetic acid 1 TOTAL 100 TOTAL 100

[0182] Component A and component B are mixed, in a volume ratio of 1:1 using a Sulzer® mixpac mixer at room temperature of 23°C. Example 2#: preparation of composition no. 2

[0183] In a mixer maintained under constant agitation and under nitrogen, the ingredients of component A are mixed in the proportions indicated in the following table at a temperature of 23°C.

[0184] In a mixer 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.

[0185] [Tables2] Composition No. 2 Component A Component B ingredients % by weight (relative to the total weight of A) ingredients % by weight (relative to the total weight of B) Trimethylolpropane formal acrylate (SR® 531) 96.8 Trimethylolpropane formal acrylate (SR® 531) 99 Speedcure® 939 2 Vanax® 808 HP 1 Cu(Acac)2 0.2 Difluoroacetic acid 1 TOTAL 100 TOTAL 100

[0186] Component A and component B are mixed, in a volume ratio of 1:1 using a Sulzer® mixpac mixer at room temperature of 23°C. Example 3#: preparation of composition no. 3

[0187] In a mixer maintained under constant agitation and under nitrogen, the ingredients of component A are mixed in the proportions indicated in the following table at a temperature of 23°C.

[0188] In a mixer maintained under constant 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.

[0189] [Tables3] Composition No. 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) Trimethylolpropane formal acrylate (SR® 531) 96.8 Trimethylolpropane formal acrylate (SR® 531) 99 Speedcure® 939 2 Vanax® 808 HP 1 Cu(OAc)2 0.2 Difluoroacetic acid 1 TOTAL 100 TOTAL 100

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

[0191] Example 4: preparation of composition no. 4 (comparative example with MMA)

[0192] In a mixer maintained under constant agitation and under nitrogen, the ingredients of component A are mixed in the proportions indicated in the following table at a temperature of 23°C.

[0193] In a mixer maintained under constant 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.

[0194] [Tables4] Composition No. 4 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 96.8 MMA 99 Speedcure® 939 2 Vanax® 808 HP 1 Cu(Acac)2 0.2 Difluoroacetic acid 1 TOTAL 100 TOTAL 100

[0195] Component A and component B are mixed, in a volume ratio of 1:1 using a Sulzer® mixpac mixer at room temperature of 23°C. Example 5#: Performance of compositions

[0196] The bonding tests were carried out under the following conditions:

[0197] - Deposition of composition No. 1, No. 2, No. 3, No. 4, (obtained respectively in the examples 1, 2, 3, 4 by mixing components A and B with a Sulzer® mixpac mixer) on a 1st glass microscope slide (25 x 76 mm);

[0198] - Display of a 2nd glass microscope slide (25 x 76 mm) on the 1st slide having received composition no. 1, no. 2, no. 3 or no. 4;

[0199] - Step of sliding the two microscope slides to allow distribution equal of composition No. 1, No. 2, No. 3, or No. 4 between the two blades (exposure to oxygen is reduced here).

[0200] The time from which it is no longer possible to separate the two blades is noted.

[0201] Reactivity (exotherm) is analyzed continuously using a pyrometer and thermal imaging. Gel time (or lag time) is the time it takes for the sample to begin to polymerize.

[0202] 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.

[0203] The results are collected in the following table:

[0204] [Tables5] Composition Gel time (s) Peak temperature (in °C) Time for bonding for a thickness of 300 microns Remarks Composition n°1 (example 1) 10 min 110 °C 12 min tacky Composition n°2 (example 2) 26 s 120 °C 1 min 30s tacky Composition No. 3 (example 3) 34 s 100°C 1 min 30 s tacky Composition No. 4 (example 4 - comparison) Unpolymerized — unpolymerized -

[0205] It is clear from this table that compositions No. 1, No. 2 and No. 3 (according to the invention) advantageously polymerize quickly (after mixing components A and B), in view of the gel times which are short (10 min, 26s and 34s, respectively). The gel times are advantageously significantly shorter in the presence of copper complex. On the other hand, it was observed that comparative composition No. 4 (example 4) does not polymerize in the open air.

[0206] Furthermore, compositions No. 1, No. 2 and No. 3 advantageously lead to bonds having rapid setting times in comparison with comparative composition No. 4.

Claims

1. Claims Crosslinkable two-component composition comprising: - a component A comprising: - an iodonium salt - an organic or mineral acid having a pKa or pKal ranging from 0.3 to 5 measured in water at 25°C; - at least one (meth)acrylate monomer Ml having one of the formulas (II), (III) or (IV) following: [Chem. 16] in which: - R3 represents H or a methyl; - R4 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; - optionally a copper salt of formula (VI) or a copper complex of formula (V-2): [Chem. 16] in which: - R and R” each represents, independently of one another, an alkyl radical, a cycloalkyl radical, an aryl radical, a heteroaryl radical, - R' represents a hydrogen atom, an alkyl radical, a cycloalkyl radical, an aryl radical, a heteroaryl radical, or R and R' (or R' and R”) 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); - a component B comprising at least one dihydropyridine compound having one of the following formulae (VI) to (X): [Chem. 17] (VBII) (VI)

2.

3. OX) (X) in which: - each of R5 to R11 represents, independently of one another, a hydrogen, an alkyl, an alkenyl, an alkynyl, a cycloalkyl, a heterocycloalkyl, a heteroaryl, an aryl, an alkylaryl, an arylalkyl, a radical -COORa; said alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, heteroaryl, aryl, alkylaryl, arylalkyl groups being optionally substituted; and Ra representing an alkyl or aryl radical; - or two radicals from R5 to R11 together form a mono- or polycyclic ring, optionally substituted; said crosslinkable two-component composition not comprising peroxide, said iodonium salt being (4-Isopropylphenyl)(4-methylphenyl)iodonium tetrakis(pentafluorophenyl)borate. Composition according to claim 1, in which the total content of iodonium salt ranges from 0.05% to 5.0% by weight, preferably from 0.1% to 3.0% by weight, even more preferably from 0.1% to 1.5% by weight relative to the total weight of the crosslinkable two-component composition. Composition according to any one of claims 1 to 2, characterized in that the (meth)acrylate monomer Ml is chosen from the following monomers: (IH-E-

4. Composition according to any one of claims 1 to 3, characterized in that the total content of (meth)acrylate monomer(s) M1 ranges from 20% to 99% by weight, preferably from 50% to 99% by weight, even more preferably from 75% to 99% by weight relative to the total weight of said crosslinkable two-component composition.

5. Composition according to any one of claims 1 to 4, characterized in that the copper salt of formula (VI) is

6.

7. copper acetate, and the copper complex of formula (V-2) is copper acetylacetonate. Composition according to any one of claims 1 to 5, characterized in that the dihydropyridine compound has the formula (IX) or (X) as defined in claim 1. Composition according to any one of claims 1 to 6, characterized in that the dihydropyridine compound is chosen from the following compounds: H 'o,x 'yy "a" X!T'" H

8. Composition according to any one of claims 1 to 7, characterized in that the molar ratio of dihydropyridine compound(s) of formula (VI) to (X) / iodonium salt(s) ranges from 0.25 to 9, preferably from 0.5 to 6, and even more preferably from 0.9 to 3 in said composition.

9. Composition according to any one of claims 1 to 8, characterized in that the acid having a pka or pkal ranging from 0.3 to 5, is an organic acid chosen from carboxylic acids, and even more preferably chosen from acrylic acid, methacrylic acid, itaconic acid, salicylic acid, benzoic acid, monochloroacetic acid, monofluoroacetic acid, dichloroacetic acid, difluoroacetic acid and mixtures thereof.

10. Composition according to any one of claims 1 to 9, characterized in that the acid has a pka or pkal ranging from 2 to 5, and in particular from 4 to 5.

11. Use of a composition as defined according to one of claims 1 to 10, as an adhesive, sealant or coating, preferably as an adhesive.

12. Method for assembling two substrates by bonding, comprising: - coating on at least one of the two substrates to be assembled a composition obtained by mixing components A and B as defined according to any one of claims 1 to 10; then - effectively bringing the two substrates into contact; and - crosslinking the composition.