Two-component composition

Abstract

The invention relates to a two-component composition comprising: - a component A comprising: - optionally alkoxylated benzyl methacrylate, - an organic zinc salt, and - a tertiary aromatic amine; and - a component B comprising: - an organic peroxide. The present invention also relates to the use of the two-component composition according to the invention as a coating or an adhesive. The present invention further relates to a method for assembling substrates, comprising: - coating at least one surface of the substrates to be assembled with the two-component composition according to the invention, then - bringing the substrates into contact, then - crosslinking the composition. Finally, the present invention relates to an article comprising the two-component composition according to the invention, said composition binding at least two substrates of said article.

Description

[0001] Two-component composition

[0002] Scope of the invention

[0003] The present invention relates to a two-component composition and its use, a method for assembling substrates and an article.

[0004] Technical background

[0005] Acrylic compositions are known reactive systems that crosslink by radical polymerization. Radical polymerization is typically initiated by a redox system which, through a redox reaction, leads to the production of radicals. Since the majority of acrylic systems are two-component systems, the first component traditionally contains the reducing agent and reactive monomers, and the second component the oxidizing agent.

[0006] The monomers usually used, mainly methyl methacrylate (MMA), have the disadvantage of being odorous when applied, generating discomfort for the user.

[0007] Alternatives to these odorous monomers have been developed. However, they generally lead to mechanical and / or reactivity properties inferior to those observed with MMA-based compositions.

[0008] In particular, the adhesion strength (especially shear strength) on polycarbonate is reduced when MMA is replaced by a low-odor acrylic monomer. However, adhesion to polycarbonate is essential in the electronics industry because polycarbonate is increasingly used as a substrate in this field.

[0009] Therefore, there is a need to provide a low-odor acrylic composition with high adhesion strength, particularly shear strength, on polycarbonate. Ideally, the acrylic composition should also have good reactivity to ensure a short setting time, and preferably be non-CMR (carcinogenic, mutagenic, reprotoxic).

[0010] Furthermore, high adhesion strength must be maintained even after aging (e.g., storage at 40°C) to prevent the substrate from unexpectedly detaching. Therefore, the acrylic composition offers advantageous storage stability.

[0011] Summary of the invention The present invention relates to a two-component composition comprising:

[0012] - a component A comprising:

[0013] - benzyl methacrylate, optionally alkoxylated,

[0014] - an organic zinc salt, and

[0015] - a tertiary aromatic amine, and

[0016] - a component B comprising:

[0017] - an organic peroxide.

[0018] The present invention also relates to the use of the two-component composition according to the invention as a coating or adhesive, preferably as an adhesive.

[0019] The present invention also relates to a method for assembling substrates comprising:

[0020] - coating, on at least one surface of the substrates to be assembled, with the two-component composition according to the invention, then

[0021] - bringing the substrates into contact, then

[0022] - cross-linking of the composition.

[0023] Finally, the present invention relates to an article comprising the two-component composition according to the invention, said composition binding at least two substrates of said article.

[0024] The present invention addresses the aforementioned needs. In particular, the two-component composition according to the invention has a low odor and high shear strength on polycarbonate, even after aging.

[0025] Description of the invention

[0026] The composition according to the invention is a two-component composition, that is, a composition separated into two parts to prevent it from self-polymerizing. A first part, in this case component A, comprises a polymerizable compound (such as benzyl methacrylate) and a reducing agent (such as a tertiary aromatic amine), while a second part, in this case component B, comprises an oxidizing agent (such as an organic peroxide). The initiation of the polymerization reaction can therefore only occur when component A is brought into contact with component B: in the present invention, the tertiary aromatic amine (the reducing agent) will react, particularly at room temperature (for example, between 18°C ​​and 25°C), with the organic peroxide (the oxidizing agent) to create free radicals that will initiate polymerization.

[0027] Benzyl methacrylate

[0028] Component A comprises benzyl methacrylate, which is a weakly odorous monomer. The benzyl methacrylate may optionally be alkoxylated, preferably non-alkoxylated.

[0029] The term "alkoxylated" can be defined as comprising at least one alkoxy group (usually obtained by reaction with an alkylene oxide), preferably ethoxy and / or propoxy, more preferably ethoxy. When benzyl methacrylate is ethoxylated, it comprises at least one ethoxy group, i.e., -(CH2CH2O) n -, in which n is different from 0. When benzyl methacrylate is propoxylated, it comprises at least one -(CH(CH3)CH2O) group m - and / or -(CH2CH(CH3)O) m -, in which m is different from 0 and may be identical or different in each group if the propoxylated benzyl methacrylate comprises both -(CH(CH3)CH2O) m - and -(CH2CH(CH3)O) m -,

[0030] When benzyl methacrylate is alkoxylated, it can include between 1 and 50 alkoxy groups (including ethoxy and / or propoxy) per molecule.

[0031] The content of benzyl methacrylate (optionally alkoxylated) may be between 20% and 80% by weight relative to the total weight of component A, preferably between 30% and 70% by weight, more preferably between 40% and 60% by weight.

[0032] Within the framework of the invention, the ranges of values ​​are understood to include the limits. For example, the range "between 0% and 25%" includes, in particular, the values ​​0% and 25%.

[0033] Organic zinc salt

[0034] Component A comprises an organic zinc salt, which may be in anhydrous or hydrated form.

[0035] The organic zinc salt may be chosen from zinc carboxylates, zinc sulfonates, and mixtures thereof, preferably from zinc carboxylates and mixtures thereof.

[0036] Zinc carboxylate can be represented by formula (I) or (II):

[0037] (RC(=O)-O-)2, Zn 2+ (L)

[0038] R-(C(=O)-O-)2, Zn 2+ (II) wherein R represents a hydrocarbon radical, saturated or unsaturated, linear or branched, optionally comprising a ring which may be aromatic and optionally one or more heteroatoms, preferably without heteroatoms. Preferably, R comprises 1 to 13 carbon atoms, more preferably 1 to 9 carbon atoms, even more preferably 1 to 5 carbon atoms, in particular 1 to 3 carbon atoms.

[0039] Zinc carboxylate preferably has the formula (I).

[0040] For example, zinc carboxylate may be selected from zinc acrylate, zinc methacrylate, zinc acetate, zinc propionate, zinc butyrate, zinc pivalate, zinc valerate, zinc hexanoate, zinc octanoate, zinc nonanoate, zinc neodecanoate, zinc maleate, zinc itaconate, zinc azelate, and mixtures thereof. Preferably, zinc carboxylate is selected from zinc acrylate, zinc methacrylate, zinc acetate, zinc propionate, and mixtures thereof, particularly from zinc methacrylate, zinc acetate, and mixtures thereof.

[0041] Zinc sulfonate can be represented by formula (III) or (IV):

[0042] (R'-S(=O)2-O-)2, Zn 2+ (III)

[0043] R'-(S(=O)2-Q-)2, Zn 2+(IV) wherein R' represents a hydrocarbon radical, saturated or unsaturated, linear or branched, optionally comprising a ring which may be aromatic and optionally one or more heteroatoms, preferably without heteroatoms. Preferably, R' comprises from 1 to 18 carbon atoms, more preferably from 1 to 6 carbon atoms.

[0044] For example, zinc sulfonate can be chosen from zinc methane sulfonate, zinc dodecane sulfonate, zinc octadecane sulfonate, and mixtures thereof.

[0045] According to a preferred embodiment, the organic zinc salt has formula (I) in which R represents a saturated or unsaturated, linear or branched hydrocarbon radical, optionally comprising a ring that may be aromatic and not comprising a heteroatom, R comprising 1 to 5 carbon atoms, in particular 1 to 3 carbon atoms. Preferably, the organic zinc salt is selected from zinc acrylate, zinc methacrylate, zinc acetate, zinc propionate, and mixtures thereof, in particular from zinc methacrylate, zinc acetate, and mixtures thereof. The content of the organic zinc salt may be from 0.1% to 10% by weight relative to the total weight of component A, preferably from 0.3% to 5% by weight, more preferably from 0.5% to 3% by weight.

[0046] Tertiary aromatic amine

[0047] The tertiary aromatic amine may be chosen from p-toluidine derivatives, aniline derivatives, N,N-dimethylaminomethylphenol, and mixtures thereof, preferably from p-toluidine derivatives and mixtures thereof.

[0048] For example, the tertiary aromatic amine can be chosen from N,N-dimethyl-p-toluidine, alkoxylated p-toluidines (such as N,N-dihydroxyethyl-p-toluidine, N-(2-hydroxyethyl)-N-methyl-p-toluidine, 2-{[2-(2-hydroxyethoxy)ethyl](4-methylphenyl)amino}ethanol, N,N-di(2-hydroxypropyl)-toluidine), N,N-dimethylaniline, N,N-dimethyl-p-chloroaniline, N,N-dimethyl-p-bromoaniline, N,N-diethyl-p-chloroaniline, N,N-diethyl-p-bromoaniline, alkoxylated anilines (such as N,N-bis(2-hydroxypropyl)-p-aniline, N-(2-hydroxyethyl)-N-methylaniline, N,N-di(2-hydroxypropyl)-p-chloroaniline, N,N-di(2-hydroxypropyl)-p-bromoaniline), N,N-dimethylaminomethylphenol, and mixtures thereof.

[0049] Advantageously, the tertiary aromatic amine is chosen from alkoxylated p-toluidines, alkoxylated anilines, and mixtures thereof, preferably from alkoxylated p-toluidines and mixtures thereof, more preferably from ethoxylated p-toluidines, propoxylated p-toluidines, and mixtures thereof, in particular from ethoxylated p-toluidines and mixtures thereof.

[0050] An alkoxylation can be defined as the introduction of one or more ether groups, for example by the reaction of a primary or secondary amine with an epoxide, particularly propylene oxide and / or ethylene oxide. When a primary or secondary amine reacts with ethylene oxide, this leads to the formation of an ethoxylated amine comprising at least one ethoxy group: -(CH2CH2O) n-, in which n is different from 0. When a primary or secondary amine reacts with propylene oxide, this leads to the formation of a propoxylated amine comprising at least one propoxy group: - (CH(CH3)CH2O) m - and / or -(CH2CH(CH3)O) m -, in which m is different from 0 and can be identical or different in each group if the amine includes both -(CH(CH3)CH2O) m - and -(CH2CH(CH3)O) m -,

[0051] When the tertiary aromatic amine is alkoxylated, it advantageously comprises between 1 and 50 alkoxy groups (particularly ethoxy and / or propoxy) per molecule, preferably between 1 and 15, more preferably between 1 and

[0052] 5.

[0053] The content of tertiary aromatic amine may be between 0.1% and 7% by weight relative to the total weight of component A, preferably between 0.3% and 5% by weight, more preferably between 0.5% and 3% by weight.

[0054] Advantageously, component A further comprises a (meth)acrylate polymer, preferably a (meth)acrylate oligomer.

[0055] In this text, "(meth)acrylate" means methacrylate or acrylate.

[0056] The term “oligomer” is known to those skilled in the art and can be defined as a small polymer, for example comprising 2 to 30 repeating units.

[0057] Advantageously, the (meth)acrylate polymer comprises between two and six (meth)acrylate groups, preferably exactly two (meth)acrylate groups. Preferably, the (meth)acrylate polymer is a methacrylate polymer.

[0058] The (meth)acrylate polymer can have a number-average molecular weight between 500 g / mol and 20,000 g / mol, preferably between 700 g / mol and 10,000 g / mol, for example between 800 g / mol and 6,500 g / mol. The number-average molecular weight can be determined by size-exclusion chromatography (SEC), for example using polystyrene reference standards and tetrahydrofuran as the solvent.

[0059] The (meth)acrylate polymer can have a glass transition temperature (Tg) below 30°C, preferably below 0°C, for example between -60°C and -5°C. The Tg can be determined by dynamic mechanical analysis (DMA).

[0060] There are many (meth)acrylate polymers available commercially, notably from SARTOMER.

[0061] The (meth)acrylate polymer may be selected from urethane (meth)acrylate polymers, polyester (meth)acrylate polymers, epoxy (meth)acrylate polymers, polyether (meth)acrylate polymers, and mixtures thereof, preferably from urethane (meth)acrylate polymers and mixtures thereof. Preferably, the (meth)acrylate polymer is a (meth)acrylate oligomer selected from urethane (meth)acrylate oligomers, polyester (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyether (meth)acrylate oligomers, and mixtures thereof, more preferably from urethane (meth)acrylate oligomers and mixtures thereof, in particular methacrylate oligomers and mixtures thereof. • Urethane (meth)acrylate polymer

[0062] The urethane (meth)acrylate polymer can be obtained by reaction between a polyol, preferably a diol, and a polyisocyanate, preferably a diisocyanate, thus forming one or more urethane (-OC(=O)-NH-) bonds, followed by functionalization with a (meth)acrylate.

[0063] The polyol can be aliphatic or aromatic, preferably aliphatic. The polyol can be a polyether polyol (such as polyethylene glycol, polypropylene glycol) and / or a polyester polyol, preferably a polyether polyol, in particular polypropylene glycol.

[0064] Polyisocyanate can be aliphatic or aromatic, preferably aromatic. Examples of polyisocyanates include 1,2-ethylene diisocyanate, 1,3-propylene diisocyanate, 1,4-butylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,8-diisocyanatooctane, 1,9-diisocyanatononane, isophorone diisocyanate, 2,4-diisocyanato-1-methylcyclohexane, 1,3-diisocyanato-2-methylcyclohexane, 1,2- and / or 1,4-cyclohexylene diisocyanate, 4,4'- and / or 2,4'-dicyclohexylmethane diisocyanate, 2,4- and / or 2,6-toluene diisocyanate, 4,4'- and / or 2,4'- diphenylmethane diisocyanate, m-xylylene diisocyanate, m-xylylene hydrogen diisocyanate and / or tetramethylxylene diisocyanate, preferably 2,4- and / or 2,6-toluene diisocyanate, 4,4'- and / or 2,4'-diphenylmethane diisocyanate, m-xylylene diisocyanate and / or tetramethylxylene diisocyanate.

[0065] The (meth)acrylate used for functionalization can be a hydroxyalkyl (meth)acrylate, for example hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxypentyl (meth)acrylate and / or hydroxyhexyl (meth)acrylate. Said (meth)acrylate is preferably a methacrylate.

[0066] • Polyester (meth)acrylate polymer

[0067] The polyester (meth)acrylate polymer can be obtained by reaction between a polycarboxylic acid, preferably a dicarboxylic acid, and a polyol, preferably a diol, thus forming a polyester polyol, preferably a polyester diol, having several ester bonds, followed by esterification with (meth)acrylic acid, preferably methacrylic.

[0068] Polyester polyol can be aliphatic or aromatic.

[0069] • Epoxy (meth)acrylate polymer

[0070] The epoxy (meth)acrylate polymer can be obtained by (meth)acrylation of a polyepoxide polymer, preferably diepoxided. The polyepoxide polymer can be aliphatic or aromatic. For example, the polyepoxide polymer can be polyepoxided bisphenol A, polyepoxided polybutadiene, and / or a polyepoxided polyunsaturated oil.

[0071] The (meth)acrylate polymer content may be between 5% and 40% by weight relative to the total weight of component A, preferably between 10% and 35% by weight, more preferably between 15% and 30% by weight.

[0072] Core-bark charge

[0073] Component A may further include a core-shell charge.

[0074] Core-shell fillers can generally be described as polymeric substances, typically in particulate form, comprising a core (inner part) comprising (or essentially consisting of) a core polymer and a shell (outer part) comprising (or essentially consisting of) a shell polymer. One or more intermediate polymer layers may be included between the core and shell polymers. By "essentially consisting of" is meant that the core (or shell) advantageously comprises less than 5% by weight of compounds other than the core (or shell) polymer relative to the total weight of the core (or shell), preferably less than 2% by weight, and more preferably less than 1% by weight.

[0075] Generally, the shell polymer has a higher glass transition temperature than the core polymer. The glass transition temperature of the core-shell filler polymers can be measured according to ISO 11357-2, for example, with a heating rate of 20°C / min. Typically, the glass transition temperature of the core polymer is below 10°C, preferably below 0°C, and more preferably below -20°C. Typically, the glass transition temperature of the shell polymer is above 60°C, preferably above 80°C, and more preferably above 100°C.

[0076] Unless otherwise stated, the standards mentioned throughout the application are those in effect on the date the application was filed.

[0077] The core polymer may comprise a polymer (homopolymer and / or copolymer) of a conjugated diene having from 4 to 12, preferably from 4 to 8, carbon atoms (such as isoprene and / or butadiene), and / or a polymer (homopolymer and / or copolymer) of an acyclic alkyl (meth)acrylate in which the alkyl chain (linear or branched) has from 1 to 12, preferably from 1 to 8, carbon atoms (such as butyl acrylate). Advantageously, the core polymer comprises (or is substantially composed of) a polymer of a conjugated diene selected from isoprene, butadiene, and mixtures thereof, preferably butadiene. Preferably, the core polymer comprises (or is essentially made up of) an isoprene homopolymer, a butadiene homopolymer, an isoprene-butadiene copolymer, a butadiene-styrene copolymer and / or an isoprene-styrene copolymer, more preferably a butadiene homopolymer and / or a butadiene-styrene copolymer.

[0078] By "essentially constituted", it is understood that the core polymer advantageously comprises less than 5% by weight of polymer(s) other than the polymer(s) mentioned above relative to the total weight of the core polymer, preferably less than 2% by weight, more preferably less than 1% by weight.

[0079] The core polymer can be crosslinked. The crosslinking agent(s) / monomer(s) can be selected from polyfunctional vinylaromatic compounds such as divinylbenzene and divinyltoluene, polyhydric alcohols such as ethylene glycol di(meth)acrylate and 1,3-butanediol di(meth)acrylate, tri(meth)acrylates, allyl carboxylates such as allyl acrylate and allyl methacrylate, and di- and triallylic compounds such as diallyl phthalate, diallyl sebacate and triallyl triazine.

[0080] The bark polymer may comprise a polymer (homopolymer and / or copolymer) of an acyclic alkyl (meth)acrylate in which the alkyl chain (linear or branched) comprises from 1 to 12 carbon atoms, preferably from 1 to 8 carbon atoms, more preferably from 1 to 4 carbon atoms, such as methyl methacrylate.

[0081] Advantageously, the bark polymer comprises (or is essentially made of) a homopolymer and / or a copolymer of an acyclic alkyl (meth)acrylate selected from methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and mixtures thereof, preferably methyl methacrylate.

[0082] In particular, the bark polymer comprises (or is substantially composed of) a methyl methacrylate homopolymer and / or a copolymer comprising at least 70% by weight of repeating motifs derived from methyl methacrylate relative to the total weight of said copolymer.

[0083] By "essentially constituted", it is understood that the bark polymer advantageously comprises less than 5% by weight of polymer(s) other than the aforementioned polymer(s) relative to the total weight of the bark polymer, preferably less than 2% by weight, more preferably less than 1% by weight.

[0084] When one or more intermediate polymer layers are present, each intermediate polymer may comprise a polymer (homopolymer and / or copolymer) of an acyclic alkyl (meth)acrylate in which the alkyl chain (linear or branched) comprises from 1 to 12 carbon atoms, preferably from 1 to 8 carbon atoms, more preferably from 1 to 4 carbon atoms, such as methyl methacrylate. Each intermediate polymer may be identical to or different from the shell polymer.

[0085] Advantageously, the intermediate polymer comprises (or is essentially made up of) a homopolymer and / or a copolymer of an acyclic alkyl (meth)acrylate selected from methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and mixtures thereof, preferably methyl methacrylate.

[0086] In particular, the intermediate polymer comprises (or is essentially made up of) a methyl methacrylate homopolymer and / or a copolymer comprising at least 70% by weight of repeating units derived from methyl methacrylate relative to the total weight of said copolymer.

[0087] By "essentially constituted", it is understood that the intermediate polymer advantageously comprises less than 5% by weight of polymer(s) other than the aforementioned polymer(s) relative to the total weight of the intermediate polymer, preferably less than 2% by weight, more preferably less than 1% by weight.

[0088] The bark polymer and / or intermediate polymer (if present) may further comprise functional groups different from the groups derived from the polymerization of an acyclic alkyl (meth)acrylate (i.e., different from the acyclic alkyl esters remaining after polymerization of said alkyl (meth)acrylate). These functional groups can be selected from epoxy groups (such as the glycidyl group), carboxylic acid groups, carboxamide groups (such as N,N-dialkylcarboxamide groups, notably N,N-dimethylcarboxamide), alkoxy groups (such as methoxy, ethoxy), amine groups (e.g. primary amine), cycloalkyl ester groups (e.g. C8-C12 cycloalkyl such as isobornyl ester, 3,3,5-trimethylcyclohexyl, tert-butylcyclohexyl and / or (octahydro-4,7-methano-1 H-indenyl)methyl), and mixtures thereof.Preferably, the functional group is derived from a functional (meth)acrylate; for example, it can be introduced by grafting the polymer to be functionalized (bark polymer, intermediate polymer(s)) with a functional (meth)acrylate or by introducing a functional (meth)acrylate during the polymerization of the polymer to be functionalized. Said functional (meth)acrylate can be selected from glycidyl (meth)acrylate, (meth)acrylic acid, (meth)acrylic acid amides (such as dimethylacrylamide), 2-methoxyethyl (meth)acrylate, (meth)acrylates comprising a primary amine (such as 2-aminoethyl (meth)acrylate), cycloalkyl (meth)acrylates (for example, C8-C12 cycloalkyl), and mixtures thereof.

[0089] Each of the bark polymers and intermediate(s) can be crosslinked. The crosslinking agent(s) / monomer(s) can be selected from polyfunctional vinylaromatic compounds such as divinylbenzene and divinyltoluene, polyhydric alcohols such as ethylene glycol di(meth)acrylate and 1,3-butanediol di(meth)acrylate, tri(meth)acrylates, allyl carboxylates such as allyl acrylate and allyl methacrylate, and di- and triallylic compounds such as diallyl phthalate, diallyl sebacate and triallyl triazine.

[0090] According to one embodiment, the core-bark charge comprises:

[0091] - a core comprising (or consisting essentially of) a core polymer comprising (or consisting essentially of) a butadiene homopolymer and / or a butadiene-styrene copolymer,

[0092] - a bark comprising (or consisting essentially of) a bark polymer comprising (or consisting essentially of) a methyl methacrylate homopolymer and / or methyl methacrylate copolymer, in particular comprising at least 70% by weight of repeating units derived from methyl methacrylate relative to the total weight of said polymer, and

[0093] - optionally one or more intermediate polymer layers, each layer comprising (or consisting essentially of) an intermediate polymer comprising (or consisting essentially of) a methyl methacrylate homopolymer and / or methyl methacrylate copolymer, in particular comprising at least 70% by weight of repeating motifs derived from methyl methacrylate relative to the total weight of said polymer.

[0094] The average volume diameter of the core-shell charge (functionalized or not) can be between 10 and 900 nm, preferably between 20 and 700 nm, and more preferably between 20 and 500 nm. The average volume diameter can be measured by dynamic light scattering (DLS).

[0095] Examples of commercially available core-bark fillers include Clearstrength® (e.g., Clearstrength® XT100) or Durastrength® sold by Arkema, or Paraloid™ (Paraloid™ 2650A, Paraloid™ 2691 A) sold by Dow.

[0096] The core-bark content may be between 5% and 30% by weight relative to the total weight of component A, preferably between 7% and 25% by weight, more preferably between 10% and 22% by weight.

[0097] Acrylic block copolymer

[0098] Component A may further comprise an acrylic block copolymer.

[0099] By "acrylic block copolymer" is meant a block copolymer comprising at least one acrylic block, that is to say, comprising at least one block consisting of a polymer obtained from at least one acrylic monomer. By "acrylic monomer" is meant in particular a monomer comprising a group of formula -X-(C=O)-C(R')=CH2, in which R' represents a hydrogen atom or a methyl radical, and -X- represents -O- or -NR"- with R" representing a hydrogen atom or an alkyl radical (cyclic, linear or branched) comprising from 1 to 22 carbon atoms, preferably from 1 to 14, more preferably from 1 to 8. Preferably, -X- represents -O-.

[0100] By "block copolymer" we mean a copolymer comprising polymer blocks, that is to say, polymer sequences that are chemically different from each other and linked together by a covalent bond.

[0101] Advantageously, the acrylic block copolymer is not obtained from styrene; preferably, the acrylic block copolymer comprises only (meth)acrylic blocks (i.e., all its blocks are obtained from (meth)acrylic monomer(s)), more preferably than alkyl (meth)acrylate blocks, each block optionally further comprising one or more monomers selected from (meth)acrylic acid, (meth)acrylic acid amides (e.g., dialkyl(meth)acrylamides such as N,N-dimethylacrylamide), amino (meth)acrylates (e.g., (meth)acrylates comprising a primary amine, such as 2-aminoethyl (meth)acrylate), epoxy (meth)acrylates (such as glycidyl (meth)acrylate), hydroxy (meth)acrylates (such as polyethylene glycol (meth)acrylate), alkoxy (meth)acrylates (such as 2-methoxyethyl (meth)acrylate), and their mixtures.

[0102] Advantageously, the acrylic block copolymer comprises at least one block A and at least one block B, block A being a polymer comprising the methyl methacrylate monomer (i.e., methyl methacrylate is the sole monomer or one of the monomers used to obtain the polymer), and block B being a polymer not comprising the methyl methacrylate monomer. Preferably, the acrylic block copolymer is a diblock copolymer AB or a triblock copolymer ABA (the two A blocks being obtained from the same or different monomers), more preferably a triblock copolymer ABA.

[0103] Preferably, block A is a polymer obtained from a mixture of monomers comprising at least 50% by weight of methyl methacrylate relative to the total weight of the monomer mixture, more preferably at least 75% by weight.

[0104] It is understood that "mixture of monomers" refers to a mixture consisting of one or more monomers; therefore, when calculating the total weight of the mixture of monomers, ingredients other than monomers (used during polymerization such as solvents, surfactants, etc.) are not taken into account.

[0105] When block A is a methyl methacrylate copolymer, the other monomer(s) constituting said copolymer may be selected from methyl acrylate, ethyl (meth)acrylate, (meth)acrylic acid, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, (meth)acrylic acid amides (e.g., dialkyl(meth)acrylamides such as N,N-dimethylacrylamide), 2-methoxyethyl(meth)acrylate, 2-aminoethyl(meth)acrylate, glycidyl (meth)acrylate, polyethylene glycol (meth)acrylate (PEG (meth)acrylate) where the PEG group has a molar mass ranging from 400 to 10000 g / mol, and their mixtures.

[0106] Preferably, block B is a polymer having a glass transition temperature (Tg) below 0°C, more preferably below -20°C. The Tg can be measured by differential scanning calorimetry (DSC).

[0107] Block B may be a polymer obtained from a mixture of monomers comprising at least 50% by weight of one or more monomers selected from ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, 2-ethylhexyl methacrylate, and mixtures thereof, relative to the total weight of the monomer mixture, preferably at least 50% by weight of n-butyl acrylate, more preferably at least 75% by weight of n-butyl acrylate.

[0108] Examples of acrylic block copolymers include the Nanostrength® products marketed by Arkema (such as M52, M75, and M65). The total content of acrylic block copolymer can be up to 30% by weight relative to the total weight of component A, preferably up to 20% by weight, and more preferably up to 10% by weight.

[0109] Other monofunctional (meth)acrylate monomer (M)

[0110] Component A may further comprise a monofunctional (meth)acrylate monomer (M) (i.e. comprising exactly one (meth)acrylate group) other than benzyl methacrylate (optionally alkoxylated).

[0111] In this text, and unless otherwise stated (such as "exactly one"), "one" means one or more.

[0112] Advantageously, the monofunctional (meth)acrylate monomer (M) has the formula: CH2=C(R a )-COOR b , in which:

[0113] - R arepresents a hydrogen atom or a methyl group, preferably a methyl group,

[0114] - R b represents an aliphatic or aromatic hydrocarbon group comprising optionally one or more groups selected from ether, ester, hydroxyl, carbonyl, and mixtures thereof, preferably R b represents an aliphatic or aromatic hydrocarbon group (not including a heteroatom), more preferably an alkyl group.

[0115] In this text, "alkyl" means an acyclic or cyclic aliphatic hydrocarbon group (i.e., comprising an aliphatic ring), not comprising a carbon-carbon double bond.

[0116] When R b represents an alkyl group, the monofunctional (meth)acrylate monomer (M) can be chosen from C1-C22 (meth)acrylate alkyls, preferably C1-C12 (meth)acrylate alkyls.

[0117] In this text, "alkyl (meth)acrylate in CX-CY" means an alkyl ester of (meth)acrylic acid in which the alkyl contains X to Y carbon atoms.

[0118] In this text, "(meth)acrylic acid" means methacrylic acid or acrylic acid.

[0119] For example, the monofunctional (meth)acrylate monomer (M) can be chosen from methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-octyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-decyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, hexadecyl (meth)acrylate, octadecyl (meth)acrylate, tricyclodecanemethanol (meth)acrylate, isobornyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate (CAS 7398-56-3), (octahydro-4,7-methano-1 H- indenyl)methyl (meth)acrylate (CAS 127823-21-6), benzyl acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, hydroxyethyl (meth)acrylate,Hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxypentyl (meth)acrylate, hydroxyhexyl (meth)acrylate, and mixtures thereof.

[0120] The benzyl methacrylate (optionally alkoxylated) content is advantageously at least 75% by weight relative to the total weight of monofunctional (meth)acrylate monomers present in component A, preferably at least 90% by weight, more preferably at least 95% by weight, even more preferably at least 99% by weight, for example 100% by weight.

[0121] The total content of monofunctional (meth)acrylate monomer (M) may be up to 15% by weight relative to the total weight of component A, preferably up to 7% by weight, more preferably up to 3% by weight.

[0122] Component A Additives

[0123] Component A may further comprise one or more additives selected from crosslinking agents, adhesion promoters, fillers (other than a core-bark filler), thermal stabilizers, UV stabilizers (or antioxidants), plasticizers, rheological agents, pigments, solvents, and mixtures thereof.

[0124] Advantageously, component A comprises a mixture of additives selected from adhesion promoters and rheological agents.

[0125] The total content of additives may be up to 30% by weight relative to the total weight of component A, preferably between 1% and 20% by weight.

[0126] The crosslinking agent can be a multifunctional (meth)acrylate. For example, the crosslinking agent may be chosen from polyethylene glycol di(meth)acrylates (such as diethylene, triethylene and / or tetraethylene glycol di(meth)acrylate), polypropylene glycol di(meth)acrylates (such as dipropylene glycol di(meth)acrylate), hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tetramethylene glycol di(meth)acrylate, di(pentamethylene glycol) di(meth)acrylate, ethylene di(meth)acrylate, bisphenol A di(meth)acrylate, bisphenol F di(meth)acrylate, and mixtures thereof.

[0127] The crosslinking agent content can be up to 5% by weight relative to the total weight of component A.

[0128] The adhesion promoter may be selected from among silanes (such as aminosilanes, epoxilanes, acryloyl silanes), phosphate ester-based adhesion promoters (such as mono-, di- and tri-esters of 2-hydroxyethyl (meth)acrylate phosphate), (meth)acrylic acid, (meth)acrylic acid amides (especially N,N-dialkylamides of (meth)acrylic acid such as N,N-dimethylacrylamide), calcium di(meth)acrylate, magnesium di(meth)acrylate, and mixtures thereof, preferably from among methacrylate phosphate ester-based adhesion promoters, (meth)acrylic acid, and mixtures thereof, especially a mixture of 2-hydroxyethyl methacrylate phosphate ester(s) and methacrylic acid.

[0129] The content of adhesion promoter can be up to 5% by weight relative to the total weight of component A, preferably between 0.5% and 4% by weight.

[0130] The filler can be chosen from organic fillers, mineral fillers, and mixtures thereof.

[0131] As an example of mineral fillers, one can cite any mineral filler commonly used in adhesive compositions. These fillers typically take the form of particles with various geometries. They can be, for example, spherical, fibrous, or irregularly shaped.

[0132] The mineral filler can be chosen from clays (such as talc), quartz, carbonate fillers (especially calcium carbonate, which can be coated with fatty acids (the latter preferably being precipitated)), kaolins, gypsum, hollow mineral microspheres (especially hollow glass microspheres, such as those made of sodium and calcium borosilicate or aluminosilicate), zeolites, and mixtures thereof.

[0133] The mineral feed can be untreated or treated, for example with an organic acid including stearic acid.

[0134] The average particle size of the mineral charge can range from 10 nm to 400 pm, preferably from 20 nm to 100 pm, more preferably from 30 nm to 50 pm.

[0135] In this text, the average particle size advantageously corresponds to the d50 particle size, i.e. the maximum size of 50% of the smallest particles by volume, and can be measured with a particle size analyzer, in particular by laser diffraction on a MALVERN type device (for example according to ISO 13320).

[0136] As an example of an organic filler, one can cite any organic filler, especially polymeric, commonly used in the field of adhesive compositions.

[0137] The organic filler can be selected from polyvinyl chloride (PVC), polyolefins, ethylene vinyl acetate (EVA), expandable or non-expandable thermoplastic polymer hollow microspheres (such as vinylidene chloride / acrylonitrile hollow microspheres), aramid fibers (such as Kevlar®), and mixtures thereof.

[0138] The average particle size of the organic load may be less than or equal to 50 pm, preferably between 5 and 20 pm.

[0139] The filler content can be up to 10% by weight relative to the total weight of component A.

[0140] The thermal stabilizer can be chosen from hydroquinone, methylhydroquinone, 2,6-di-tert-butyl-4-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol (BHT), 2,4-dimethyl-6-tert-butylphenol (Topanol A).

[0141] The thermal stabilizer content can be up to 3% by weight relative to the total weight of component A.

[0142] A UV stabilizer is typically introduced to prevent degradation resulting from a reaction with oxygen, which can be formed by the action of heat or light. UV stabilizers may include antioxidants capable of scavenging free radicals.

[0143] The UV stabilizer (or antioxidant) can be chosen from among benzotriazoles, benzophenones, phosphites (such as tris(2,4-di-tert-butylphenyl)phosphite), so-called hindered phenols (such as rethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], 2,2'-methylenebis(6-(tert-butyl)-4-methylphenol), 2,2'-methylenebis(6-(tert-butyl)-4-ethylphenol), 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(4,6-di(tert-butyl)phenol), 4,4'-methylenebis(2,6-di(tert-butyl)phenol, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,6-di(tert-butyl)-4-methylphenol), so-called hindered amines (such as bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate (CAS No: 41556-26-7), methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate (CAS No 82919-37-7), 4,4'-bis(α,α-dimethylbenzyl)diphenylamine), and mixtures thereof.

[0144] The LIV stabilizer (or antioxidant) content can be up to 3% by weight relative to the total weight of component A.

[0145] The plasticizer can be any plasticizer commonly used in the field of adhesives.

[0146] For example, the plasticizer can be chosen from epoxy resins (such as those based on bisphenol A diglycidyl ether), alkyl phthalates (such as diisodecyl phthalate, diisononyl phthalate, diisononyl hexahydrophthalate), benzoates (such as nonylbenzoate), alkylsulfonic acid and phenol esters (such as MESAMOLL® by LANXESS), pentaerythritol tetravalerate, diisononyl-1,2-cyclohexanedicarboxylate, 3,3-methylenebis(oxymethylene)]bis[heptane], dioctyl carbonate, hydrocarbon oils (also called mineral oils, generally obtained from petroleum, such as paraffinic oils, naphthenic oils), natural oils (possibly epoxidized, such as epoxidized soybean oil), polypropylene, polybutylene, hydrogenated polyisoprene, and their mixtures.

[0147] The plasticizer content can be up to 8% by weight relative to the total weight of component A.

[0148] The rheological agent may be chosen from among thixotropic agents, for example from: fumed silica (hydrophilic and / or hydrophobic), urea derivatives from the reaction of a diisocyanate monomer, preferably aromatic such as diphenylmethylene diisocyanate (in particular 4,4'-MDI), with a primary aliphatic amine such as butylamine, waxes derived from castor oil, such as THIXCIN® R by ELEMENTIS, amide waxes, preferably micronized, such as CRAYVALLAC® SLT by ARKEMA, beeswax (in particular CAS 8006-40-4 and / or 8012-89-3), and mixtures thereof.

[0149] By "waxes derived from castor oil" we mean waxes obtained from castor oil, in particular hydrogenated castor oil.

[0150] The term "amide waxes" refers to waxes comprising one or more compounds with at least one amide group. In particular, amide waxes can be obtained from organic acid(s) (e.g., fatty acid(s)) and (di)amine(s).

[0151] The amide waxes are preferably micronized, that is to say, they have an average particle size of less than 1 mm. Advantageously, the amide waxes have an average particle size of less than 500 pm, preferably less than 100 pm, more preferably less than 15 pm.

[0152] Preferably, the rheological agent chosen from among fumed silica, amide waxes, and mixtures thereof, in particular a mixture of hydrophobic fumed silica and amide wax.

[0153] The content of rheological agent can be up to 15% by weight relative to the total weight of component A, preferably between 3% and 10% by weight.

[0154] The pigment can be chosen from organic pigments, inorganic pigments, and mixtures thereof. For example, the pigment can be chosen from phthalocyanine-based pigments (such as copper phthalocyanine, halogenated copper phthalocyanine, metal-free phthalocyanine), anthraquinone-based pigments (such as 1-methylamino-4-o-tolylaminoanthraquinone, 1,4-diisopropyl aminoanthraquinone, 1,4-diaminoanthraquinone, 1,4-dibutyl-aminoanthraquinone, 1-amino-4-anilinoanthraquinone), quinacridone-based pigments, perylene-based pigments, thioindigo-based pigments, quinophthalone-based pigments, titanium dioxide, carbon black, manganese ferrite, and mixtures thereof.

[0155] The pigment content can be up to 2% by weight relative to the total weight of component A.

[0156] The solvent can be any solvent suitable for acrylic adhesive compositions.

[0157] The solvent content can be up to 5% by weight relative to the total weight of component A.

[0158] Organic peroxide

[0159] A peroxide is a compound comprising a single oxygen-oxygen bond.

[0160] Organic peroxide can be chosen from organic hydroperoxides (such as cumene hydroperoxide, t-butyl hydroperoxide, p-menthane hydroperoxide, methyl ethyl ketone peroxide), peroxyesters (such as t-butyl peroxyneodecanoate, t-butyl peroxybenzoate, t-butyl peroxyisobutyrate, t-amyl peroxypivalate, t-butyl peroxyacetate), peroxydicarbonates (such as dicyclohexyl peroxydicarbonate), diacyl peroxides (such as diacetyl peroxide, dibenzoyl peroxide, dilauroyl peroxide), dihydrocarbon peroxides (such as dicumyl peroxide, t-butylcumyl peroxide), polyperoxides (such as 1,3-bis-(t- butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di-t-butylperoxyhexane, 2,2-di-t-butylperoxy pentane), peracids (such as peracetic acid, perbenzoic acid), and mixtures thereof, preferably among the diacyl peroxides, for example dibenzoyl peroxide.

[0161] The organic peroxide content may be between 10% and 40% by weight relative to the total weight of component B, preferably between 12% and 30% by weight.

[0162] The organic peroxide content in component B may be between 1% and 4% by weight relative to the total weight of the two-component composition, preferably between 1.1% and 3% by weight.

[0163] The ratio by weight of tertiary aromatic amine / organic peroxide can be between 0.2 and 5, preferably between 0.3 and 2.

[0164] Component B Additives

[0165] Component B may further include one or more additives selected from adhesion promoters, fillers (other than a core-bark filler), thermal stabilizers, UV stabilizers (or antioxidants), plasticizers, rheological agents, pigments, solvents, and mixtures thereof.

[0166] Advantageously, component B comprises a mixture of additives selected from plasticizers and rheological agents.

[0167] The total content of additives can be up to 90% by weight relative to the total weight of component B, preferably between 70% and 88% by weight.

[0168] The total content of additives in component B may be up to 9% by weight relative to the total weight of the two-component composition, preferably between 6% and 8% by weight.

[0169] The adhesion promoter may be chosen from aminosilanes, epoxilanes, phosphate ester-based adhesion promoters (other than those comprising an acrylic group), and mixtures thereof.

[0170] The adhesion promoter content can be up to 5% by weight relative to the total weight of component B.

[0171] The filler can be chosen from organic fillers, mineral fillers, and mixtures thereof. As an example of mineral fillers, one could cite any mineral filler commonly used in adhesive compositions. These fillers typically come in the form of particles of various geometries. They can, for example, be spherical, fibrous, or irregularly shaped.

[0172] The mineral filler can be chosen from clays (such as talc), quartz, carbonate fillers (especially calcium carbonate, which can be coated with fatty acids (the latter preferably being precipitated)), kaolins, gypsum, hollow mineral microspheres (especially hollow glass microspheres, such as those made of sodium and calcium borosilicate or aluminosilicate), zeolites, and mixtures thereof.

[0173] The mineral feed can be untreated or treated, for example with an organic acid including stearic acid.

[0174] The average particle size of the mineral charge can range from 10 nm to 400 pm, preferably from 20 nm to 100 pm, more preferably from 30 nm to 50 pm.

[0175] As an example of an organic filler, one can cite any organic filler, especially polymeric, commonly used in the field of adhesive compositions.

[0176] The organic filler can be selected from polyvinyl chloride (PVC), polyolefins, ethylene vinyl acetate (EVA), expandable or non-expandable thermoplastic polymer hollow microspheres (such as vinylidene chloride / acrylonitrile hollow microspheres), aramid fibers (such as Kevlar®), and mixtures thereof.

[0177] The average particle size of the organic load may be less than or equal to 50 pm, preferably between 5 and 20 pm.

[0178] The filler content can be up to 10% by weight relative to the total weight of component B.

[0179] The thermal stabilizer can be chosen from hydroquinone, methylhydroquinone, 2,6-di-tert-butyl-4-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol (BHT), 2,4-dimethyl-6-tert-butylphenol (Topanol A).

[0180] The thermal stabilizer content can be up to 1% by weight relative to the total weight of component B.

[0181] The UV stabilizer (or antioxidant) can be chosen from among benzotriazoles, benzophenones, phosphites (such as tris(2,4-di-tert-butylphenyl)phosphite), so-called hindered phenols (such as those indicated above for component A), so-called hindered amines (such as those indicated above for component A), and mixtures thereof.

[0182] The LIV stabilizer (or antioxidant) content can be up to 1% by weight relative to the total weight of component B.

[0183] The plasticizer can be any plasticizer commonly used in the field of adhesives.

[0184] For example, the plasticizer can be chosen from epoxy resins (such as those based on bisphenol A diglycidyl ether), alkyl phthalates (such as diisodecyl phthalate, diisononyl phthalate, diisononyl hexahydrophthalate), benzoates (such as nonylbenzoate), alkylsulfonic acid and phenol esters (such as MESAMOLL® by LANXESS), pentaerythritol tetravalerate, diisononyl-1,2-cyclohexanedicarboxylate, 3,3-methylenebis(oxymethylene)bis[heptane], dioctyl carbonate, hydrocarbon oils (also called mineral oils, generally obtained from petroleum, such as paraffinic oils, naphthenic oils), polyalkylene glycols (in particular those having a polymer backbone based on ethylene glycol and / or propylene glycol monomers, such as poly(ethylene) glycol-ran-propylene glycol), monobutyl ether), natural oils (possibly epoxidized, such as epoxidized soybean oil), polypropylene,Polybutylene, hydrogenated polyisoprene, and mixtures thereof. Preferably, the plasticizer is selected from benzoates, polyalkylene glycols, natural oils, and mixtures thereof, particularly from alkylbenzoates, polyalkylene glycols, epoxidized natural oils, and mixtures thereof.

[0185] The plasticizer content can be up to 90% by weight relative to the total weight of component B, preferably between 20% and 85% by weight.

[0186] The rheological agent may be chosen from among thixotropic agents, for example from: fumed silica (hydrophilic and / or hydrophobic), urea derivatives from the reaction of a diisocyanate monomer, preferably aromatic such as diphenylmethylene diisocyanate (in particular 4,4'-MDI), with a primary aliphatic amine such as butylamine, waxes derived from castor oil, such as THIXCIN® R by ELEMENTIS, amide waxes, preferably micronized, such as CRAYVALLAC® SLT by ARKEMA, beeswax (in particular CAS 8006-40-4 and / or 8012-89-3), and mixtures thereof.

[0187] The amide waxes are preferably micronized, that is to say, they have an average particle size of less than 1 mm. Advantageously, the amide waxes have an average particle size of less than 500 pm, preferably less than 100 pm, more preferably less than 15 pm.

[0188] Preferably, the rheological agent is chosen from among the amide waxes.

[0189] The content of rheological agent can be up to 10% by weight relative to the total weight of component B, preferably between 1% and 7% by weight.

[0190] The pigment can be chosen from organic pigments, inorganic pigments, and mixtures thereof. For example, the pigment can be chosen from phthalocyanine-based pigments (such as copper phthalocyanine, halogenated copper phthalocyanine, metal-free phthalocyanine), anthraquinone-based pigments (such as 1-methylamino-4-o-tolylaminoanthraquinone, 1,4-diisopropyl aminoanthraquinone, 1,4-diaminoanthraquinone, 1,4-dibutyl-aminoanthraquinone, 1-amino-4-anilinoanthraquinone), quinacridone-based pigments, perylene-based pigments, thioindigo-based pigments, quinophthalone-based pigments, titanium dioxide, carbon black, manganese ferrite, and mixtures thereof.

[0191] The pigment content can be up to 5% by weight relative to the total weight of component B.

[0192] The solvent can be any solvent suitable for acrylic adhesive compositions.

[0193] The solvent content can be up to 8% by weight relative to the total weight of component B.

[0194] Other characteristics of the two-component composition

[0195] Advantageously, the volume ratio of component A to component B is between 1 and 20, preferably between 5 and 15, for example about 10.

[0196] By "approximately X", we are aiming for more or less 10% of the value of X.

[0197] According to one embodiment, the two-component composition according to the invention comprises:

[0198] - a component A comprising:

[0199] - between 20% and 80% by weight of benzyl methacrylate, optionally alkoxylated, - between 0.1% and 10% by weight of an organic zinc salt, the organic zinc salt preferably being chosen from zinc carboxylates and mixtures thereof,

[0200] - between 0.1% and 7% by weight of a tertiary aromatic amine,

[0201] - between 5% and 40% by weight of a (meth)acrylate polymer,

[0202] - optionally between 5% and 30% by weight of core-bark filler,

[0203] - optionally up to 20% by weight of acrylic block copolymer,

[0204] - optionally up to 15% by weight of a monofunctional (meth)acrylate monomer (M) other than optionally alkoxylated benzyl methacrylate, and

[0205] - optionally up to 30% by weight of one or more additives selected from crosslinking agents, adhesion promoters, fillers (other than a core-bark filler), thermal stabilizers, LIV stabilizers (or antioxidants), plasticizers, rheological agents, pigments, solvents, and mixtures thereof, relative to the total weight of component A, and

[0206] - a component B comprising:

[0207] - between 10% and 40% by weight of an organic peroxide, and

[0208] - up to 90% by weight of one or more additives chosen from adhesion promoters, fillers (other than a core-bark filler), thermal stabilizers, LIV stabilizers (or antioxidants), plasticizers, rheological agents, pigments, solvents, and mixtures thereof, relative to the total weight of component B, the volume ratio of component A to component B being between 1 and 20.

[0209] Preferably, the two-component composition according to the invention consists essentially of the ingredients mentioned above. By "consists essentially of" means that the two-component composition according to the invention comprises less than 5% by weight of ingredients other than the aforementioned ingredients, relative to the total weight of said composition, preferably less than 2% by weight, and even more preferably less than 1% by weight.

[0210] The ingredients of this embodiment and their particular contents are as described above, including preferred embodiments and characteristics.

[0211] In particular, the two-component composition according to the invention comprises: - a component A comprising:

[0212] - between 40% and 60% by weight of benzyl methacrylate, optionally alkoxylated, preferably non-alkoxylated,

[0213] - between 0.5% and 3% by weight of an organic zinc salt, the organic zinc salt preferably being chosen from zinc acrylate, zinc methacrylate, zinc acetate, zinc propionate, and mixtures thereof,

[0214] - between 0.1% and 7% by weight of a tertiary aromatic amine, the tertiary aromatic amine preferably being chosen from alkoxylated p-toluidines, alkoxylated anilines, and mixtures thereof,

[0215] - between 15% and 30% by weight of a (meth)acrylate polymer, the (meth)acrylate polymer preferably being chosen from among the (meth)acrylate urethane polymers,

[0216] - optionally between 10% and 22% by weight of core-bark filler,

[0217] - optionally up to 10% by weight of acrylic block copolymer,

[0218] - optionally up to 3% by weight of a monofunctional (meth)acrylate monomer (M) other than optionally alkoxylated benzyl methacrylate, and

[0219] - optionally between 1% and 20% by weight of one or more additives chosen from crosslinking agents, adhesion promoters, fillers (other than a core-bark filler), thermal stabilizers, UV stabilizers (or antioxidants), plasticizers, rheological agents, pigments, solvents, and mixtures thereof, relative to the total weight of component A, and

[0220] - a component B comprising:

[0221] - between 12% and 30% by weight of an organic peroxide, the organic peroxide preferably being chosen from among the diacyl peroxides, and

[0222] - between 70% and 88% by weight of one or more additives chosen from adhesion promoters, fillers (other than a core-bark filler), thermal stabilizers, UV stabilizers (or antioxidants), plasticizers, rheological agents, pigments, solvents, and mixtures thereof, component B preferably comprising a mixture of additives chosen from plasticizers and rheological agents, relative to the total weight of component B, the volume ratio of component A to component B being between 5 and 15. Preferably, the two-component composition according to the invention consists essentially of the ingredients mentioned above.

[0223] The ingredients of this embodiment and their particular contents are as described above, including preferred embodiments and characteristics.

[0224] Advantageously, the two-component composition according to the invention has a shear strength on polycarbonate (preferably before and after aging) of at least 6 MPa, preferably between 7 MPa and 12 MPa. The shear strength can be measured according to ISO 4587 (2003), for example as shown in Example 1 below. The properties after aging can be evaluated after separate storage of components A and B for 1 month, for example as shown in Example 1 below.

[0225] Each of the components A and B of the two-component composition according to the invention can be prepared separately by simply mixing its ingredients. An example of preparation is described in Example 2 below.

[0226] Components A and B can be packaged, for example, in a twin cartridge protected from air and moisture. The composition according to the invention can then be obtained by attaching a mixer, for example a static mixer, to the end of the twin cartridge.

[0227] Use of the

[0228] The present invention also relates to the use of the two-component composition according to the invention as a coating or adhesive, preferably as an adhesive (in particular a structural adhesive, for example resistant to a shear stress greater than or equal to 7 MPa at 23°C), in particular in the field of building construction, in the field of manufacturing means of transport (such as the automotive, railway, aerospace, naval industries), electronics, assembly, wind power or construction.

[0229] The two-component composition according to the invention is as described above, including preferred embodiments and features.

[0230] Substrate assembly process

[0231] The present invention also relates to a method for assembling substrates comprising: - coating, on at least one surface of the substrates to be assembled, with the two-component composition according to the invention as described above (including preferred embodiments and features), then

[0232] - bringing the substrates into contact, then

[0233] - cross-linking of the composition.

[0234] The two-component composition according to the invention is as described above, including preferred embodiments and features.

[0235] It is understood that, during the coating and contacting stages, the two-component composition according to the invention is in the non-crosslinked state.

[0236] The crosslinking step can be carried out at a temperature between 10°C and 40°C, preferably between 15°C and 30°C, particularly at room temperature (for example between 18°C ​​and 25°C).

[0237] The substrates can be identical or different.

[0238] A wide variety of substrates can be used. These can include, for example, plastic, glass, metal, and / or composite materials. Preferably, at least one substrate is plastic, and more preferably, all substrates are plastic.

[0239] The plastic can be PVC, polycarbonate, polymethyl methacrylate (PMMA), polystyrene and / or acrylonitrile butadiene styrene (ABS), preferably polycarbonate and / or ABS, especially polycarbonate.

[0240] The metal can be pure or an alloy, for example aluminium and / or steel (including stainless steel and / or galvanised).

[0241] The composite can be a reinforced plastic material, such as a fiber-reinforced plastic, particularly a sheet-molded composite (SMC). The fibers in the fiber-reinforced plastic can be glass, carbon, aramid, or basalt fibers, preferably glass fibers. The fiber length can vary from 6 mm to 50 mm. The polymer in the reinforced plastic material can be a polyester, polyolefin, epoxy, or vinyl ester resin. The polymer in the reinforced plastic material is preferably unsaturated. The reinforced plastic material may include other compounds besides the fibers and the polymer (such as fillers and / or catalysts).

[0242] Article

[0243] The present invention also relates to an article comprising the two-component composition according to the invention (in the crosslinked or non-crosslinked state) as described above (including preferred embodiments and features), said composition bonding at least two substrates of said article.

[0244] The article can be obtained through the substrate assembly process according to the invention (including preferred embodiments and features).

[0245] The substrates are preferably as described above for the substrate assembly process according to the invention, in particular the substrates are preferably made of plastic, especially polycarbonate.

[0246] For example, the item could be a part of an electronic device (computer, phone, television, ...).

[0247] All the embodiments described above can be combined with one another. In particular, the various aforementioned components of the composition, and especially the preferred embodiments, can be combined with one another.

[0248] The following examples are given purely to illustrate the invention and should not be interpreted as limiting its scope.

[0249] Examples

[0250] Example 1: Ingredients and measurement methods

[0251] Ingredients used

[0252] The following ingredients were used:

[0253] - VISIOMER® BNMA (by Evonik): benzyl methacrylate,

[0254] - MERACRYL® HEMA 98 (by Rohm): 2-hydroxyethyl methacrylate,

[0255] - VISIOMER® GLYFOMA (by Evonik): glycerol methacrylate form (mixture of isomers, CAS: 1620329-57-8),

[0256] - Oligomer: urethane dimethacrylate oligomer, obtained from polypropylene glycol (hydroxyl value of approximately 55.5 mg KOH / g according to ASTM D4274) and tolylene diisocyanate and functionalized with hydroxyethyl methacrylate,

[0257] - Bisomer® PTE (by Geo Specialty Chemicals): mixture of ethoxylated para-toluidines (CAS: 103671-44-9), tertiary aromatic amine,

[0258] - Clearstrength® XT 100 (by Arkema): core-bark filler,

[0259] - Methacrylic acid (by Sigma-Aldrich),

[0260] - SR9054 (by SARTOMER): methacrylate mixture including phosphate groups, adhesion promoter, - AEROSIL® R 202 (by Evonik): hydrophobic fumed silica (treated with dimethyl polysiloxane), rheological agent,

[0261] - CRAYVALLAC® SLT (by Arkema): micronized amide wax, rheological agent,

[0262] - DYMALINK® 708 (by Cray Valley, a Total company): zinc methacrylate (CAS: 13189-00-9), organic zinc salt,

[0263] - Zinc acetate (by Sigma-Aldrich): CAS: 557-34-6, organic zinc salt,

[0264] - PEROXAN BP-Paste 50 PF 1 (by PERGAN): 50% dibenzoyl peroxide paste, organic peroxide,

[0265] - Vikoflex® 7170 (by Cargill): epoxy soybean oil (CAS: 8013-07-8), plasticizer.

[0266] Measurement methods

[0267] Lap Shear Strength (LSS) was measured according to ISO 4587 (2003). A 250 µm layer of the test composition was applied between two 2 mm thick polycarbonate sheets. Shear strength was measured at 23°C, after 24 hours of curing at 23°C and 50% humidity, and the fracture surface was recorded (a semi-cohesive, semi-adhesive fracture was noted as RSC). The shear stress was applied using a tensile testing machine at a constant rate of 5 mm / min.

[0268] The peak time corresponds to the time required to observe the exothermic peak (maximum temperature) of the crosslinking reaction. The reactivity of the compositions was monitored using a thermocouple probe. The two-component cartridge was first purged, and then the components were mixed with a static mixer. After purging the mixture, 30 g were placed in a perforated container, and the temperature probe was inserted to monitor the exothermic reaction and record the temperature over time. At the end of the test, the exothermic peak was determined to be the maximum observed temperature.

[0269] The post-aging properties were evaluated in accordance with the tests described above, except that component A was stored for 1 month in an oven at 40°C and component B was stored at room temperature (approximately 23°C) before carrying out the tests.

[0270] The odor of the compositions was evaluated blindly on component A by a group of 3 people and averaged: component A was placed in a sealed bottle for 48 hours, then the odor was evaluated upon opening the bottle. A score was assigned from 1 to 4 (1: light odor, 2: medium odor, 3: strong odor, 4: very strong odor).

[0271] Example 2: Preparation of compositions according to the invention and comparative compositions

[0272] Compositions 1-7 were prepared by introducing one component 1A-7A and one component B into a two-cartridge container (protected from air and moisture), then mixing them using a static mixer attached to the end of the container, at room temperature (23°C) with a volume ratio A / B of 10. The component A used in each composition is described in Table 1 below, with the values ​​shown being weight percentages relative to the total weight of component A. Component B is the same for compositions 1-7 and consists of:

[0273] - 29% of PEROXAN BP-Paste 50 PF 1,

[0274] - 66% of Vikoflex® 7170, and

[0275] - 5% of CRAYVALLAC ® SLT, the percentages being percentages by weight relative to the total weight of component B.

[0276] Components A and B were prepared separately by mixing their ingredients by centrifugation until homogenized (SpeedMixer™ mixer).

[0277] [Table 1] Example 3: Properties of the compositions prepared in Example 2

[0278] The properties of the compositions prepared in Example 2 were evaluated according to the methods described in Example 1, and the results are shown in Table 2.

[0279] [Table 2]

[0280] NA: Not applicable, ND: Not determined, Manual: Peels off by hand

[0281] Compositions 1 to 7 all have a low odor (score below 1.5). In contrast, a composition based on methyl methacrylate (approximately 50% by weight relative to the total weight of component A) has a strong odor (score above 3).

[0282] The addition of an organic zinc salt (DYMALINK® 708 or zinc acetate) significantly improves the reactivity of a benzyl methacrylate-based composition, both before and after aging. Specifically, the peak time decreased from approximately 40 minutes for the comparative composition 1 (without organic zinc salt) to less than 10 minutes for compositions 1 and 2 according to the invention.

[0283] Furthermore, unlike comparative composition 1, compositions 2 and 3 according to the invention retain high shear strength values ​​on polycarbonate, even after aging.

[0284] However, comparative compositions 4 and 5 based on 2-hydroxyethyl methacrylate (MERACRYL® HEMA 98, low-odor monomer) exhibit zero shear strength on polycarbonate, even though they contain an organic zinc salt. Furthermore, while the addition of zinc dimethacrylate (DYMALINK® 708) improves the initial shear strength on polycarbonate of a composition based on glycerol formal methacrylate (VISIOMER® GLYFOMA, low-odor CMR monomer), this effect is not observed after aging. Indeed, comparative composition 7 has improved initial shear strength compared to comparative composition 6, but the polycarbonate substrate assembly detaches by hand after aging. Therefore, comparative composition 7 is not stable during storage because the adhesion does not persist over time.

[0285] Thus, unlike comparative compositions, the combination of benzyl methacrylate and an organic zinc salt makes it possible to obtain adhesive compositions that are both low odor, non-CMR, crosslinking rapidly, and have high adhesion to polycarbonate even after aging.

Claims

Demands 1. Two-component composition comprising: - a component A comprising: - benzyl methacrylate, optionally alkoxylated, - an organic zinc salt, and - a tertiary aromatic amine, and - a component B comprising: - an organic peroxide.

2. Two-component composition according to claim 1, wherein the organic zinc salt is selected from zinc carboxylates and mixtures thereof.

3. Two-component composition according to claim 2, wherein the zinc carboxylate is selected from zinc acrylate, zinc methacrylate, zinc acetate, zinc propionate, zinc butyrate, zinc pivalate, zinc valerate, zinc hexanoate, zinc octanoate, zinc nonanoate, zinc neodecanoate, zinc maleate, zinc itaconate, zinc azelate, and mixtures thereof, preferably from zinc methacrylate, zinc acetate, and mixtures thereof.

4. Two-component composition according to any one of claims 1 to 3, wherein the tertiary aromatic amine is selected from alkoxylated p-toluidines, alkoxylated anilines, and mixtures thereof, preferably from alkoxylated p-toluidines and mixtures thereof.

5. Two-component composition according to any one of claims 1 to 4, wherein component A further comprises a (meth)acrylate polymer.

6. Two-component composition according to claim 5, wherein the (meth)acrylate polymer is selected from urethane (meth)acrylate polymers, polyester (meth)acrylate polymers, epoxy (meth)acrylate polymers, polyether (meth)acrylate polymers, and mixtures thereof, preferably from urethane (meth)acrylate polymers and mixtures thereof.

7. Two-component composition according to any one of claims 1 to 6, wherein component A further comprises a core-shell filler.

8. Two-component composition according to any one of claims 1 to 7, wherein the content of optionally alkoxylated benzyl methacrylate is at least 75% by weight relative to the total weight of monofunctional (meth)acrylate monomers present in component A.

9. Use of the two-component composition according to any one of claims 1 to 8 as a coating or adhesive, preferably as an adhesive.

10. Substrate assembly method comprising: - coating, on at least one surface of the substrates to be assembled, with the two-component composition according to any one of claims 1 to 8, then - bringing the substrates into contact, then - cross-linking of the composition.

11. Article comprising the two-component composition according to any one of claims 1 to 8, said composition bonding at least two substrates of said article.

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