Composition based on (meth)acrylate monomers

Abstract

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; - an organic or mineral acid having a pKa or pKa1 ranging from 0.3 to 5 measured in water at 25°C; - at least one photoinitiator P1; - a component B comprising at least one dihydropyridine compound having one of the formulas (III) to (VI). This composition does not comprise a peroxide. Figure: None

Description

Title of the invention: Composition based on (meth)acrylate monomers FIELD OF 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 semi-structural or structural repair and / or bonding of materials in the fields of transport, marine, assembly, electronics, or construction. TECHNOLOGICAL BACKGROUND

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

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

[0005] Typically, (meth)acrylic compositions comprise a peroxide (oxidant) / tertiary amine (reducer) type redox system. However, these systems may present stability problems with regard to storage 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] In addition, there is also a need for new (meth)acrylic compositions having good adhesive properties. DESCRIPTION OF THE INVENTION

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

[0013] - R1 and R2 each represent, independently of each other, 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;

[0014] - at least one monomer (meth)acrylate Ml;

[0015] - an organic or mineral acid having a pKa or pKa ranging from 0.3 to 5.0 measured in water at 25°C;

[0016] - at least one PI photoinitiator;

[0017] - a component B comprising at least one dihydropyridine compound having one of the formulas (III) to (VII) as follows:

[0019] in which:

[0020] - each of R5 to R11 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, a -COOR' radical;

[0021] said alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, heteroaryl, aryl, alkylaryl, arylalkyl groups being optionally substituted;

[0022] and Ra representing an alkyl or aryl radical;

[0023] - or two radicals from R5 to R11 together form a mono- or polycyclic cycle, possibly substituted;

[0024] said crosslinkable two-component composition not comprising peroxide.

[0025] In the context of the invention, "alkyl" means a linear or branched radical preferably comprising from 1 to 20 carbon atoms. Examples include methyl, ethyl, and propyl.

[0026] In the context of the invention, "alkenyl" means a linear or branched hydrocarbon radical comprising at least one double bond, said radical preferably comprising from 2 to 20 carbon atoms. Examples include propenyl and butenyl.

[0027] In the context of the invention, "alkynyl" means a linear or branched hydrocarbon radical comprising at least one triple bond, said radical comprising preference for 2 to 20 carbon atoms.

[0028] In the context of the invention, "aryl" means a monocyclic or bicyclic aromatic radical preferably comprising 6 to 12 carbon atoms. Phenyl is an example.

[0029] In the context of the invention, "arylalkyl" means an alkyl group substituted by an aryl group, the arylalkyl group preferably comprising 7 to 20 carbon atoms. Benzyl is an example of an arylalkyl group.

[0030] In the context of the invention, "alkylaryl" means an aryl group substituted by an alkyl group, said alkylaryl group preferably comprising from 7 to 20 carbon atoms.

[0031] In the context of the invention, "heteroaryl" means a monocyclic or bicyclic aromatic radical comprising at least one heteroatom such as, for example, O, S, or N, and preferably comprising from 4 to 12 carbon atoms. Examples include furanyl, thiophenyl, pyrrolyl, pyridinyl, indolyl, and imi-dazolyl radicals.

[0032] In the context of the invention, "cycloalkyl" means a monocyclic or polycyclic system, preferably monocyclic or bicyclic, saturated, preferably comprising 3 to 12 carbon atoms, the rings being able to be fused or bridged in pairs, such as cyclopropyl, cyclopentyl, cyclohexyl or norbornyl groups.

[0033] In the context of the invention, "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 being able to be fused or bridged in pairs.

[0034] In the context of the invention, "cycloalkenyl" means a monocyclic or polycyclic system, comprising at least one double bond, preferably comprising from 3 to 12 carbon atoms, the rings being able to be fused or bridged in pairs.

[0035] In the context of the invention, "alkoxy" means an -O-alkyl radical. Component A Iodonium salt of formula (IA), (IB) or (IC)

[0036] Component A comprises an iodonium salt having one of the formulas (LA), (LB) or (LC) as defined above.

[0037] Preferably, in the aforementioned formulas (LA), (LB) and (LC), R1 and R2 each represent, independently of each other, an alkyl radical or a hydrogen atom.

[0038] In the aforementioned formulas (LA), (LB) and (LC), X can represent F, Cl, Br , I, NO3, HSO4, H2PO4, HCOO, CH3COO, BF4, AsF6, PF6, CH3-Ph-SO3, (F5Ph)4B or SbF6. Preferably, in the above-mentioned formulas (IA), (IB) and (IC), X represents BF4, PF6, CH3-Ph-SO3, (F5Ph)4B or SbF6. Even more preferably, X represents the union (F5Ph)4B of the following formula:

[0039] [Chem.3]

[0040] Among the iodonium salts of formula (IB), we can cite for example:

[0041] [Chem.4]

[0042] Among the iodonium salts of formula (IC), we can cite for example:

[0043] [Chem.5]

[0044] Among the iodonium salts of formula (IA), examples may be cited, for example, 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.

[0045] 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:

[0046] [Chem.6]

[0047] 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.

[0048] The total content of iodonium salt of formula (IA), (IB) or (IC) can range from 0.20% to 5.0% by weight, preferably from 0.50% to 3.0% by weight, even more preferably from 0.50% to 1.5% by weight relative to the total weight of the crosslinkable two-component composition. (meth)acrylate monomer Ml

[0049] The two-component composition according to the invention comprises at least one (meth)acrylate monomer ML

[0050] The (meth)acrylate monomer may comprise one (meth)acrylate function (monofunctional) or several (meth)acrylate functions (polyfunctional).

[0051] The monomer (meth)acrylate Ml may have the following formula (II):

[0052] [Chem.7]

[0053] in which R3 represents H or methyl, G represents an organic radical preferably comprising at least one oxygen atom, and f represents an integer from 1 to 4.

[0054] In the aforementioned formula (II), G may represent a radical selected from the group consisting of alkyls, cycloalkyls, alkenyls, cycloalkenyls, alkylaryls, arylalkyls or aryls, said alkyls, cycloalkyls, alkenyls, cycloalkenyls, alkylaryls, arylalkyls or aryls being optionally substituted and / or interrupted by at least one silane, silicone, oxygen, halogen, a carbonyl, a hydroxyl, an ester, a urea, a urethane, a carbonate, an amine, an amide, a sulfur, a sulfonate, or a sulfone.

[0055] In the aforementioned formula (II), f can represent 1, 2, 3 or 4, f preferably representing 1.

[0056] The (meth)acrylate monomer(s) Ml may be chosen from the group consisting of:

[0057] - compounds having the following formula (II-1):

[0058] [Chem. 8]

[0059] in which:

[0060] - R3 represents H or methyl; - G 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 optionally substituted and / or interrupted by at least one silane, silicone, oxygen, halogen, carbonyl, hydroxyl, ester, urea, urethane, carbonate, amine, amide, sulfur, sulfonate, or sulfone;

[0061] - polyethylene glycol di(meth)acrylates;

[0062] - hexanediol di(meth)acrylate;

[0063] - of trimethylol propane tri(meth)acrylate;

[0064] - diethylene glycol di(meth)acrylate;

[0065] - triethylene glycol di(meth)acrylate;

[0066] - tetraethylene glycol di(meth)acrylate;

[0067] - dipropylene glycol di(meth)acrylate;

[0068] - di-(pentamethylene glycol di(meth)acrylate;

[0069] - diglycerol tetra(meth)acrylate;

[0070] - tetramethylene di(meth)acrylate;

[0071] - of ethylene di(meth)acrylate;

[0072] - bisphenol A mono- and di(meth)acrylates;

[0073] - bisphenol F mono- and di(meth)acrylates;

[0074] - compounds of the following formulas (VIII), (IX) or (X)

[0075] [Chem.9]

[0076] in which:

[0077] - R3 represents H or methyl;

[0078] - R4 represents H, methyl or ethyl;

[0079] - p represents 0 or 1; and

[0080] - Z represents H, O, S, an alkyl group, a benzyl group, an aryl group, or a alkoxy group;

[0081] - Y represents O, S, NH or CH2;

[0082] - a single bond or a double bond,

[0083] provided that when Z represents O, then the bond ^pjest is a double bond;

[0084] - and mixtures thereof.

[0085] Among the monomers Ml of formula (II-1), examples include methyl (meth)acrylate, ethyl (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, (meth)acrylate hexadecyl, 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, the , 3-vinylcyclohexyl (meth)acrylate, bomyl (meth)crylate, 2,4,5-tri-t-butyl-3-vinylcyclohexyl (meth)acrylate, (meth)acrylate 2,3,4,5-tetra-t-butylcyclohexyl; benzyl (meth)acrylate, phenyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, and mixtures thereof.

[0086] Among the monomers Ml of formula (VIII) mentioned above, examples may be cited:

[0087] [Chem. 10] (vm-c)

[0088] Among the monomers Ml of formula (IX) mentioned above, we can cite for example:

[0089] [Chem. 11]

[0090] (IXÆ) OX-F)

[0091] The radical G can be an organic radical comprising at least one oxygen atom.

[0092] According to a preferred embodiment, G is an organic radical comprising at least one oxygen atom, said radical G being a polar aprotic radical.

[0093] In the context of the invention, and unless otherwise stated, an aprotic radical is understood to mean a radical not comprising an acidic hydrogen.

[0094] In the context of the invention, and unless otherwise stated, a polar radical is understood to be a radical containing polar bonds whose sum of all the dipole moments of the bond is non-zero.

[0095] The monomer Ml is preferably chosen from monomers of formula (VIII) or (IX). More preferably, it is one of the following compounds or mixtures thereof:

[0096] [Chem. 12] (IX-F) (VHI-A) (IX-A)

[0097] The total content of (meth)acrylate monomer(s) Ml in component A may be greater than or equal to 30% by weight relative to the total weight of said component A.

[0098] The content of monomer(s) (meth)acrylate Ml in the crosslinkable two-component composition according to the invention can range from 30% 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

[0099] 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.

[0100] The pKa (or acidity constant) is defined by pKa = -logi0 Ka, where Ka is the constant acid dissociation is measured in a standard manner at 25°C. The standard measurement method recommended for pKa is potentiometry, and more specifically pH-metry, as described for example in engineering techniques (ref. K695 vl). This method is the most widely used for determining pKa.

[0101] The pKa is defined by pKa = -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 the polyacids (if any), and Ka3 is the acid dissociation constant of the third weakest acidity of the polyacids (if any). Each successive acidity of a polyacid corresponds, in particular, to decreasing values ​​of the acidity constants Kal, Ka2, and Ka3. The same standard potentiometric measurement described above is used to measure them.

[0102] Examples of organic acids include carboxylic acids, phosphoric acids, and mixtures thereof.

[0103] Examples of carboxylic acids include formic acid, acetic acid, monochloroacetic acid, monofluoroacetic acid, dichlo-roacetic 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, thio-glycolic acid, pyruvic acid, cinnamic acid, and mixtures thereof.

[0104] Among the mineral acids, examples include phosphoric acid, phosphorous acid, methylphosphonic acid, hypophosphorous acid, and mixtures thereof.

[0105] According to one embodiment, the acid has a pKa or pKa ranging from 2 to 5, and in particular from 4 to 5.

[0106] According to a preferred embodiment, the acid having a pKa or pkal ranging from 0.3 to 5 is an organic acid selected from carboxylic acids, and even more preferably 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.

[0107] The presence of this / these acid(s) advantageously allows the dihydropyridine compound of formulas (III) to (VII) to be activated.

[0108] The total content of acid(s) having a pKa or pKa ranging from 0.3 to 5 may range from 0.1% to 20% by weight, preferably from 0.1% to 10% by weight, preferably still from 0.2 % to 5%, and even more preferably from 0.2% to 2% by weight relative to the total weight of the two-component crosslinkable composition according to the invention. Photoinitiator PI

[0109] Component A comprises at least one photoinitiator PL

[0110] This PI photoinitiator is different from the iodonium salt of formula (LA), (LB) or (LC) as defined previously.

[0111] The photoinitiator can be any photoinitiator known to those skilled in the art. Under the action of UV-visible radiation, the photoinitiator typically generates radicals that are responsible for initiating the photopolymerization reaction, and in particular increases the efficiency of the photopolymerization reaction. It is, of course, chosen according to the light source used, based on its ability to efficiently absorb the selected radiation. For example, the appropriate photoinitiator can be chosen based on its UV-visible absorption spectrum. Advantageously, the photoinitiator is suitable for use with irradiation sources emitting in the near-field range of 300 to 420 nm. Advantageously, the UV or visible radiation source can be an LED.

[0112] The photoinitiator PI can be selected from the group consisting of:

[0113] - Type I photoinitiators selected from:

[0114] - the family of acetophenones and alkoxyacetophenones, such as for example the 2,2-dimethoxy-2-phenylacetophenone and 2-diethyl-2-phenylacetophenone;

[0115] - the hydroxyacetophenone family, such as for example the 2,2-dimethyl-2-hydroxyacetophenone, L-hydroxycyclohexylphenyl ketone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methyl-propriophenone and 2-hydroxy-4'-(2-hydroxypropoxy)-2-methyl-propriophenone;

[0116] - the alkylaminoacetophenone family, such as for example the 2-methyl-4'-(methylthio)-2-morpholino-propriophenone, 2-benzyl-2-(dimethylamino)-4-morpholinobutyrophenone and 2-(4-(methylbenzyl)-2-(dimethylamino)-4-morpholino-butyrophenone;

[0117] - the family of benzoin ethers, such as, for example, benzyl, methyl ether of benzoin and isopropyl benzoin ether;

[0118] - the family of phosphine oxides, such as, for example, diphenyl oxide- (2,4,6-trimethylbenzoyl)phosphine (TPO), ethyl-(2,4,6-trimethylbenzoyl)phenylphosphine oxide (TPO-L) and bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylphenyl phosphine oxide (BAPO);

[0119] - the family of metallocenes, such as for example ferrocene, bis(eta 5-2,4-cyclopentadien-l-yl)-bis(2,6-difluoro)-3-(lH-pyrrole-l-yl)-phenyl) of titanium and iron (cumene)cyclopentadienyl hexafluorophosphate;

[0120] - Type II photoinitiators selected from:

[0121] - the benzophenone family, such as for example 4-phenylbenzophenone, the 4-(4'-methylphenylthio)benzophenone, the l-[4[ (4-benzoylphenyl)thio]phenyl] -2-methyl-2- [(4-methylphenyl) sulfonyl] -1 -propan one;

[0122] - the thioxanthone family, such as for example isopropylthioxanthone (ITX), the 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2-chlorothioxanthone and 1-chloro-4-isopropylthioxanthone;

[0123] - the family of formate benzoyl esters, such as for example methylben- zoylformate;

[0124] - the dibenzylidene ketone family, such as for example p- dimethylaminoketone;

[0125] - the coumarin family, such as, for example, 5-methoxy coumarin and 7-methoxy, 7-diethylamino coumarin and N-phenyleglycine coumarin;

[0126] - photoinitiators from the dye family such as, for example, triazines, fluorones, cyanines, safranines, the 4,5,6,7-tetrachloro-3',6'-dihydroxy-2',4',5',7'-tetraiodo-3H-spiro[isobenzofuran-1,9'-xan then]-3-one, pyrylium and thiopyrylium, thiazines, flavins, pyronines, oxazines, rhodamines;

[0127] - and mixtures thereof.

[0128] According to a preferred embodiment, the photoinitiator PI is selected from:

[0129] - the family of phosphine oxides, such as, for example, diphenyl oxide- (2,4,6-trimethylbenzoyl)phosphine (TPO), ethyl-(2,4,6-trimethylbenzoyl)phenylphosphine oxide (TPO-L) and bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylphenyl phosphine oxide (BAPO);

[0130] - the thioxanthone family, such as for example isopropylthioxanthone (ITX), the 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2-chlorothioxanthone and 1-chloro-4-isopropylthioxanthone;

[0131] the photoinitiator PI being even more preferentially chosen from diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), and ethyl-(2,4,6-trimethylbenzoyl)phenylphosphine oxide (TPO-L).

[0132] The total content of photoinitiator(s) PI may range from 0.1% to 5% by weight, preferably from 0.1% to 2%, and even more preferably from 0.1% to 1% by weight relative to the total weight of the two-component crosslinkable composition according to the invention. Component B Dihydropyridine compound of formulas (III) to (VII)

[0133] Component B comprises at least one dihydropyridine compound having one of the

[0134]

[0135]

[0136]

[0137]

[0138]

[0139] formulas (III) to (VII) as defined above. The dihydropyridine compound may be chosen from those of formulas (III) to (VII) in which: - R11 represents an aryl or heteroaryl, said aryl or heteroaryl being even actually 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, a radical -COORa, Ra representing an alkyl; R5 to R10 preferably representing independently of each other, a hydrogen or an alkyl or a -COORa radical with Ra representing an alkyl. According to a preferred embodiment, the dihydropyridine compound has the formula (VI) or (VII) as defined previously. The dihydropyridine compound can be chosen from the following compounds: [Chem. 13]

[0140]

[0141] N"'

[0143] According to a preferred embodiment, the dihydropyridine is the following compound:

[0144]

[0145] Dihydropyridines may be commercially available such as, for example, Vanax 808 HP cillrucakusé oar VANDERBILT CHEMICALS, or may be synthesized as described, for example, in WO 2006 / 086602.

[0146] The total content of dihydropyridine compound(s) having one of the formulas (III) to (VII) as defined above may range from 0.2% to 5.0% by weight, preferably from 0.3% to 3.0% by weight, and even more preferably from 0.4% to 1.5% by weight relative to the total weight of the crosslinkable two-component composition according to the invention.

[0147] In the crosslinkable two-component composition according to the invention, the molar ratio of dihydropyridine compound(s) of formula (III) to (VII) / iodonium salt(s) of formula (LA) or (LB) or (LC) can range from 0.70 to 9, preferably from 1 to 6, and even more preferably from 1 to 3. Composition

[0148] The crosslinkable two-component composition according to the invention may include at least one additive selected from the group consisting of catalysts, fillers, antioxidants, light stabilizers / UV absorbers, metal deactivators, antistatics, anti-haze agents, foaming agents, biocides, plasticizers, lubricants, emulsifiers, colorants, pigments, rheological agents, impact modifiers, adhesion promoters, accelerators, optical brighteners, flame retardants, anti-seepage agents, nucleating agents, solvents, and mixtures thereof.

[0149] These additives may be present in component A and / or component B of the composition according to the invention.

[0150] Saccharin can be cited as an example of an accelerator.

[0151] By way of example of a usable plasticizing agent, any plasticizing agent commonly used in the field of adhesives may be cited, such as, for example, epoxy resins, phthalates, benzoates, trimethylolpropane esters, trimethylolethane esters, trimethylolmethane esters, glycerol esters, pentaerythritol esters, naphthenic mineral oils, adipates, cyclohexyldicar-boxylates, paraffinic oils, natural oils (possibly epoxidized), polypropylenes, polybutylenes, hydrogenated polyisoprenes, and mixtures thereof.

[0152] One can, for example, use:

[0153] - 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 the ARKEMA Company.

[0154] As an example of usable (thixotropic) rheology agent(s), any rheology agent commonly used in the field of adhesive compositions may be cited.

[0155] Preferably, the thixotropic agents are chosen from:

[0156] - PVC plastisols, corresponding to a suspension of PVC in a plasticizing agent miscible with PVC, obtained in situ by heating to temperatures ranging from 60°C to 80°C. These plastisols may be those described in particular in the book "Polyurethane Sealants", Robert M. Evans, ISBN 087762-998-6, - fumed silica, such as for example sold under the name HDK® N20 by WACKER; - urea derivatives resulting from the reaction of an aromatic diisocyanate monomer such as 4,4'-MDI with an aliphatic amine such as butylamine. The preparation of such urea derivatives is described in particular in application FR 1 591 172; - micronized amide waxes, such as CRAYVALLAC® SLT or CRAYVALLAC® SLA marketed by ARKEMA.

[0157] The composition according to the invention may further comprise at least one organic and / or mineral filler.

[0158] The usable mineral filler(s) is / are advantageously chosen so as to improve the mechanical performance of the composition according to the invention in the crosslinked state.

[0159] As an example of usable mineral filler(s), any mineral filler(s) commonly used in adhesive compositions may be used. These fillers typically take the form of particles of various geometries. They may, for example, be spherical, fibrous, or have an irregular shape.

[0160] 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 among carbonate fillers, such as alkali or alkaline-earth metal carbonates, and more preferably calcium carbonate or chalk.

[0161] These fillers can be untreated or treated, for example with an organic acid such as stearic acid, or a mixture of organic acids consisting mainly of stearic acid.

[0162] Hollow mineral microspheres such as hollow glass microspheres, and more particularly those made of sodium and calcium borosilicate or aluminosilicate, can also be used.

[0163] The composition according to the invention may further comprise at least one adhesion promoter, preferably selected from silanes, such as aminosilanes, epoxilanes or acryloyl silanes, or phosphate ester-based adhesion promoters such as, for example, 2-hydroxyethyl methacrylate phosphate ester, 2-methacryloyloxyethyl phosphate, bis-(2-methacryloyloxyethyl phosphate), 2-acryloyloxyethyl phosphate, bis-(2-acryloyloxyethyl phosphate), methyl-(2-methacryloyloxyethyl phosphate), ethyl-(2-methacryloyloxyethyl phosphate), a mixture of mono- and di-phosphate esters of 2-hydroxyethyl methacrylate.

[0164] When a pigment is present in the composition, its content is preferably less than or equal to 3% by weight, and more preferably less than or equal to 2% by weight, relative to the total weight of the composition. When present, the pigment may, for example, represent from 0.1% to 3% by weight or from 0.4% to 2% by weight of the total weight of the composition.

[0165] The pigments can be organic or inorganic pigments.

[0166] For example, the pigment is TiO2, in particular KRONOS® 2059 marketed by the company KRONOS.

[0167] The composition may comprise 0.1% to 3%, preferably 1% to 3% by weight, of at least one UV stabilizer or antioxidant. These compounds are typically introduced to protect the composition from degradation resulting from A reaction with oxygen that is likely to be formed by the action of heat or light. These compounds may include primary antioxidants that scavenge free radicals. Primary antioxidants can be used alone or in combination with other secondary antioxidants or UV stabilizers.

[0168] Examples include IRGANOX ® 1010, IRGANOX ® B561, IRGANOX ® 245, IRGAFOS ® 168, TINUVIN® 328 or TINUVIN™ 770 marketed by BASF.

[0169] According to a preferred embodiment, the two-component composition according to the invention does not comprise metallic acetylacetonate, such as, for example, iron acetylacetonate or copper acetylacetonate.

[0170] In the composition according to the invention, the volume ratio component A / component B can range from 20 / 1 to 1 / 1, preferably from 10 / 1 to 1 / 1. B. Ready-to-use kit

[0171] 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.

[0172] Indeed, the composition according to the invention can be found in a two-component form, for example in a ready-to-use kit, comprising component A on the one hand in a first compartment or drum and component B on the other hand in a second compartment or drum, in proportions adapted for a direct mixing of the two components, for example using a dosing pump.

[0173] 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

[0174] 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.

[0175] The invention also relates to the use of said composition for the structural or semi-structural repair and / or bonding of materials in the field of transport, automotive (car, bus or truck), assembly, marine, electronics, or construction.

[0176] The present invention relates to a method for assembling two substrates by bonding, comprising:

[0177] - coating 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 by subjecting it to electromagnetic irradiation.

[0178] Electromagnetic irradiation can be carried out on the edges of the bond in the case of an opaque substrate or directly through the substrate in the case of a transparent substrate.

[0179] 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.

[0180] Suitable substrates are, for example, inorganic substrates such as concrete, metals or alloys (such as aluminium alloys, steel, non-ferrous metals and galvanised metals); or organic substrates such as wood, plastics such as PVC, polycarbonate, PMMA, polyethylene, polypropylene, polyesters, epoxy resins; metal substrates and paint-coated composites.

[0181] Crosslinking is carried out under electromagnetic irradiation such as for example with a UV radiation source or with an LED.

[0182] The electromagnetic irradiation crosslinking step can be carried out at a wavelength greater than 300 nm, preferably from 360 nm to 680 nm, and even more preferably from 360 nm to 420 nm.

[0183] 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.

[0184] The compositions according to the invention advantageously exhibit good adhesive properties after crosslinking.

[0185] In addition, the surface of cross-linked compositions advantageously dries quickly and may not be "tacky", which in particular makes it possible to increase the productivity of industrial processes.

[0186] All the embodiments described above can be combined with each other. In particular, the various aforementioned components of the composition, and especially the preferred modes, of the composition can be combined with each other.

[0187] In the context of the invention, "between x and y" or "ranging from x to y" means an interval in which the bounds x and y are included. For example, the range "between 0% and 25%" includes, in particular, the values ​​0% and 25%.

[0188] The invention is now described in the following embodiments, which are given purely for illustrative purposes and shall not be construed to limit its scope. scope. EXAMPLES

[0189] The following ingredients were used:

[0190] - SR® 531: cyclic trimethylolpropane form acrylate (CAS: 66492-51-1) com marketed by ARKEMA;

[0191] - SPEEDCURE® 939: (4-Isopropylphenyl)(4-methylphenyl)iodonium tetrakis(pentafluorophenyl)borate (CAS: 178233-72-2) marketed by LAMBSON;

[0192] - SPEEDCURE® TPO-L (CAS: 84434-11-7) marketed by LAMBSON: ethyl (2,4,6-trimethylbenzoyl) phenyl phosphinate;

[0193] - VANAX® 808 HP: 3,5-diethyl-1,2-dihydro-1-phenyl-2-propylpyridine (CAS: 34562-31-7) marketed by VERTELLUS SPECIALITIES;

[0194] - Difluoroacetic acid (CAS: 381-73-7) available from SIGMA-ALDRICH;

[0195] Example 1: preparation of composition no. 1 with photoinitiator

[0196] 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.

[0197] In a mixer maintained under constant agitation 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.

[0198] [Tables] Composition No. 1 according to invention Component A Component B ingredients % by weight (relative to the total weight of A) ingredients % by weight (relative to the total weight of B) Trimethylolpropane formaldehyde acrylate (SR® 531) 96 Trimethylolpropane formaldehyde acrylate (SR® 531) 99 Speedcure® 939 2 Vanax® 808 HP 1 Difluoroacetic acid 1 Speedcure® TPO L 1 TOTAL 100 TOTAL 100

[0199] Component A and component B are mixed in a 1:1 volume ratio using a Sulzer® mixpac mixer at an ambient temperature of 23°C. The mixture is then irradiated under 405 nm with an intensity of 110 mW / cm2 and its reactivity evaluated in air by pyrometry.

[0200] Comparative example 2: preparation of composition no. 2 without photoinitiator

[0201] In a mixer maintained under constant stirring and under nitrogen, the ingredients of component A are mixed in the proportions indicated in the following table at a temperature of 23 °C.

[0202] In a mixer maintained under constant agitation 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.

[0203] [Tables2] Comparative 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 e-formal acrylate (SR® 531) 97 Trimethylolpropane e-formal acrylate (SR® 531) 99 Speedcure® 939 2 Vanax® 808 HP 1 Difluoracetic acid 1 TOTAL 100 TOTAL 100

[0204] Component A and component B are mixed in a volume ratio of 1:1 using a Sulzer® mixpac mixer at an ambient temperature of 23°C and its reactivity is evaluated under air by pyrometry. Example 3: Composition performance

[0205] The exotherm is continuously analyzed using a pyrometer and thermal imaging, as well as using an RT-FTIR spectrometer. The gel time (or latency time) is the time it takes for the sample to begin polymerizing.

[0206] The time / temperature profiles were obtained using an Omega OS552-V1-6 industrial infrared thermometer (Omega Engineering®, Inc., Stamford, CT) accuracy ± 1 °C for 2 g (approximately 4.0 mm height) and 0.25 g (1.4 mm height) of polymerization.

[0207] [Tables3] Composition Freezing Time (s) Peak Temperature (°C) Remarks Composition No. 1 (example 1) 3 min 40 s 140°C No residual tack Composition No. 2 (comparative example 2) 7 min 40 s 120°C Residual tack

[0208] Composition No. 1 polymerizes advantageously rapidly (after mixing components A and B), given the short gel time (3 min 40 s) compared to comparative composition No. 2 which does not include a photoinitiator (7 min 40 s).

[0209] Finally, it was observed that the polymer obtained after crosslinking is advantageously dry on the surface (no tack) for composition no. 1 compared to composition no. 2 (residual tack).

Claims

Claims

1. Crosslinkable two-component composition comprising: - a component A comprising: - an iodonium salt having one of the following formulae (IA), (IB) or (IC): [Chem. 14] 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; - at least one (meth)acrylate monomer Ml; - 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 PI photoinitiator; - a component B comprising at least one dihydropyridine compound having one of the following formulae (III) to (VII): [Chem. 15] 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.

2. Composition according to claim 1, characterized in that in formulas (IA) or (IB) or (IC), X represents F, Cl, Br, I, NO3, HSO 4, H2PO4, HCOO, CH3COO , BF4 , AsF6 , PF6, CH3-Ph-SO3, (F5Ph)4B

3.

4. or SbF6, X preferably representing BF4, PF6, CH3-Ph-SO3, SbF6 or (F5Ph)4B, and even more preferably X represents (F5Ph)4B. Composition according to any one of claims 1 or 2, characterized in that the iodonium salt of formula (IA) or (IB) or (IC) is chosen from 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, the iodonium salt preferably being (4-Isopropylphenyl)(4-methylphenyl)iodonium tetrakis(pentafluorophenyl)borate. Composition according to any one of claims 1 to 3, characterized in that the (meth)acrylate monomer Ml has the following formula (II): [Chem. 16]

5. in which R3 represents H or methyl, G represents an organic radical preferably comprising at least one oxygen atom, and f represents an integer ranging from 1 to 4. Composition according to any one of claims 1 to 4, characterized in that the (meth)acrylate monomer Ml is chosen from the group consisting of: - compounds having the following formula (II-1): [Chem. 17] Q in which: R3 represents H or methyl; - G is selected from the group consisting of alkyls, cycloalkyls, alkenyls, cycloalkenyls, alkylaryls, arylalkyls or aryls, said alkyls, cycloalkyls, alkenyls, cycloalkenyls, alkylaryls, arylalkyls or aryls possibly being 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; - 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; - compounds of the following formulas (VIII), (IX) or (X) [Chem. 18] (X) in which: - R3 represents H or 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; - ^.-5 a single bond or a double bond, provided that when Z represents 0, then the bond is a double bond; - and mixtures thereof.

6. Composition according to any one of claims 1 to 5, characterized in that G is an organic radical comprising at least one oxygen atom, said radical G being an aprotic polar radical.

7. Composition according to any one of claims 1 to 6, characterized in that the monomer Ml is chosen from the following compounds:

8. Composition according to any one of claims 1 to 7, characterized in that the content of (meth)acrylate monomer(s) Ml in the crosslinkable two-component composition ranges from 30% 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.

9. Composition according to any one of claims 1 to 8, characterized in that the photoinitiator PI is chosen from the group consisting of: - type I photoinitiators chosen from: - the family of acetophenones and alkoxyacetophenones, such as for example 2,2-dimethoxy-2-phenylacetophenone and 2-diethyl-2-phenylacetophenone; - 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; - the family of alkylaminoacetophenones, such as for example 2-methyl-4'-(methylthio)-2-morpholino-propriophenone, 2-benzyl-2-(dimethylamino)-4-morpholino-butyrophenone and 2-(4-(methylbenzyl)-2-(dimethylamino)-4-morpholino-butyrophenone - the family of benzoin ethers, such as for example benzyl, methyl benzoin ether and isopropyl benzoin ether; - 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); - the family of metallocenes, such as for example ferrocene, bis(eta 5-2,4-cyclopentadien-l-yl)-bis(2,6-difluoro)-3-(lH-pyrrole-l-yl)-phenyl) titanium and iron (cumene)cyclopentadienyl hexafluorophosphate; - type II photoinitiators chosen from: - the benzophenone family, such as for example 4-phenylbenzophenone, 4-(4'-methylphenylthio)benzophenone, l-[4[ (4-benzoylphenyl)thio]phenyl]-2-methyl-2-[(4-methylphenyl)sulfonyl]-l-propanone; - the thioxanthone family, such as for example isopropylthioxanthone (ITX), 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2-chlorothioxanthone and 1-chloro-4-isopropylthioxanthone; - the family of benzoyl formate esters, such as for example methylbenzoylformate; - 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; - photoinitiators of the family of dyes such as for example triazines, fluorones, cyanines, safranins, 4,5,6,7-tetrachloro-3',6'-dihydroxy-2',4',5',7'-tetraiodo-3H-spiro[isobenz ofuran-1,9'-xanthen]-3-one, pyrylium and thiopyrylium, thiazines, flavins, pyronins, oxazines, rhodamines; - and mixtures thereof.

10. Composition according to any one of claims 1 to 9, characterized in that the photoinitiator PI is chosen from: - 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); - the family of thioxanthones, such as for example isopropylthioxanthone (ITX), 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2-chlorothioxanthone and 1-chloro-4-isopropylthioxanthone; the photoinitiator PI being more preferably chosen from diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), and ethyl-(2,4,6-trimethylbenzoyl)phenylphosphine oxide (TPO-L).

11. Composition according to any one of claims 1 to 10, characterized in that the total content of photoinitiator(s) PI can range from 0.1% to 5% by weight, preferably from 0.1% to 2% by weight relative to the total weight of the crosslinkable two-component composition according to the invention.

12. Composition according to any one of claims 1 to 11, characterized in that the dihydropyridine compound has the formula (VI) or (VII) as defined in claim 1.

13. Composition according to any one of claims 1 to 12, characterized in that the dihydropyridine compound is chosen from the following compounds:

14. Composition according to any one of claims 1 to 13, characterized in that the molar ratio of dihydropyridine compound(s) of formula (III) to (VII) / iodonium salt(s) of formula (IA) or (IB) or (IC) ranges from 0.70 to 9, preferably from 1 to 6, and even more preferably from 1 to 3.

15. Composition according to any one of claims 1 to 14, 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 preferentially chosen from acrylic acid, methacrylic acid, itaconic acid, salicylic acid, benzoic acid, monochloroacetic acid, monofluoroacetic acid, dichloroacetic acid, difluoroacetic acid and mixtures thereof.

16. Use of a composition as defined according to one of claims 1 to 15, as an adhesive, sealant or coating, preferably as an adhesive.

17. 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 15; then - effectively bringing the two substrates into contact; and - crosslinking the composition with electromagnetic irradiation.