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 adhesive. The present invention also 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, and then - crosslinking the composition. Finally, the present invention relates to an article comprising the two-component composition according to the invention, said composition bonding at least two substrates of said article. Figure for the abstract: none

Description

Title of the invention: Two-component composition Scope of the invention

[0001] The present invention relates to a two-component composition and its use, a method for assembling substrates and an article. Technical background

[0002] 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 the reactive monomers, and the second component the oxidizing agent.

[0003] The monomers usually used, mainly methyl methacrylate (MMA), have the disadvantage of being odorous when applied, generating discomfort for the user.

[0004] 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.

[0005] In particular, the adhesion strength (especially shear strength) on polycarbonate is reduced when MMA is replaced by a slightly odorous acrylic monomer. However, adhesion to polycarbonate is essential in the electronics field because polycarbonate is increasingly used as a substrate.

[0006] There is therefore a need to provide a low-odor acrylic composition with high adhesion strength, particularly shear strength, on polycarbonate. It is preferable that the acrylic composition also have good reactivity so that the setting time is short, and preferably be non-CMR (carcinogenic, mutagenic, reprotoxic).

[0007] Furthermore, a high adhesion strength must be maintained even after aging (e.g., storage at 40°C) to prevent the substrate from unexpectedly detaching. The acrylic composition is therefore advantageously stable during storage. Summary of the invention

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

[0009] - a component A comprising:

[0010] - benzyl methacrylate optionally alkoxylated,

[0011] - an organic zinc salt, and

[0012] - a tertiary aromatic amine, and

[0013] - a component B comprising:

[0014] - an organic peroxide.

[0015] 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.

[0016] The present invention also relates to a method for assembling substrates comprising:

[0017] - coating, on at least one surface of the substrates to be assembled, the composition two-component according to the invention, then

[0018] - bringing the substrates into contact, then

[0019] - crosslinking of the composition.

[0020] 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.

[0021] 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. Description of the invention: Two-component composition

[0022] 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. Benzyl methacrylate

[0023] Component A comprises benzyl methacrylate, which is a weakly odorous monomer. The benzyl methacrylate may optionally be alkoxylated, preferably non-alkoxylated.

[0024] The term "alkoxylated" can be defined as comprising at least one alkoxy group (generally 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)m- and / or -(CH2 CH(CH3)O)m- group, 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-,

[0025] When benzyl methacrylate is alkoxylated, it can comprise between 1 and 50 alkoxy groups (in particular ethoxy and / or propoxy) per molecule.

[0026] The benzyl methacrylate (optionally alkoxylated) content can 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.

[0027] In the context 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%. Organic zinc salt

[0028] Component A comprises an organic zinc salt, which may be in anhydrous or hydrated form.

[0029] The organic zinc salt can be chosen from zinc carboxylates, zinc sulfonates, and mixtures thereof, preferably from zinc carboxylates and mixtures thereof.

[0030] Zinc carboxylate can be represented by formula (I) or (II):

[0031] (RC(=0)-0 )2, Zn2+(I)

[0032] R-(C(=0)-0)2, Zn2+(II)

[0033] 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.

[0034] Zinc carboxylate preferably has formula (I).

[0035] For example, the 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, the zinc carboxylate is selected from zinc acrylate, zinc methacrylate, zinc acetate, zinc propionate, and mixtures thereof, in particular from zinc methacrylate, zinc acetate, and mixtures thereof.

[0036] Zinc sulfonate can be represented by formula (III) or (IV):

[0037] (R' -S(=0)2-0)2, Zn2+ (III)

[0038] R' _(S(=0)2-0)2, Zn2+ (IV)

[0039] in which 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.

[0040] For example, zinc sulfonate can be selected from zinc methane sulfonate, zinc dodecane sulfonate, zinc octadecane sulfonate, and mixtures thereof.

[0041] According to a preferred embodiment, the organic zinc salt has formula (I) in which R represents a hydrocarbon radical, saturated or unsaturated, linear or branched, 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.

[0042] The organic zinc salt content may be between 0.1% and 10% 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. Tertiary aromatic amine

[0043] The tertiary aromatic amine can be chosen from p-toluidine derivatives, aniline derivatives, N,N-dimethylaminomethylphenol, and mixtures thereof, preferably from p-toluidine derivatives and mixtures thereof.

[0044] 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.

[0045] 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 p-toluidines ethoxylated, propoxylated p-toluidines, and their mixtures, in particular among ethoxylated p-toluidines and their mixtures.

[0046] An alkoxylation can be defined as the introduction of one or more ether groups, for example by reaction of a primary or secondary amine with an epoxide, in particular 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 not equal to 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 not equal to 0 and may be the same or different in each group if the amine comprises both -(CH(CH3)CH2O)m- and -(CH2CH(CH3)O)m-.

[0047] When the tertiary aromatic amine is alkoxylated, it advantageously comprises between 1 and 50 alkoxy groups (in particular ethoxy and / or propoxy) per molecule, preferably between 1 and 15, more preferably between 1 and 5.

[0048] 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. (meth)acrylate polymer

[0049] Advantageously, component A further comprises a (meth)acrylate polymer, preferably a (meth)acrylate oligomer.

[0050] In the present text, "(meth)acrylate" means methacrylate or acrylate.

[0051] 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 motifs.

[0052] 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.

[0053] The (meth)acrylate polymer may 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.

[0054] 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).

[0055] There are many (meth)acrylate polymers available commercially, notably from SARTOMER.

[0056] The (meth)acrylate polymer can 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

[0057] 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.

[0058] The polyol may be aliphatic or aromatic, preferably aliphatic. The polyol may be a polyether polyol (such as polyethylene glycol, polypropylene glycol) and / or a polyester polyol, preferably a polyether polyol, in particular polypropylene glycol.

[0059] The 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, and 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.

[0060] The (meth)acrylate used for functionalization may 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. • Polyester (meth)acrylate polymer

[0061] 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 acid.

[0062] Polyester polyol can be aliphatic or aromatic. • Epoxy (meth)acrylate polymer

[0063] The epoxy (meth)acrylate polymer can be obtained by (meth)acrylation of a polyepoxide polymer, preferably diepoxided.

[0064] The polyepoxidized polymer can be aliphatic or aromatic. For example, the polyepoxidized polymer can be polyepoxidized bisphenol A, polyepoxidized polybutadiene and / or a polyepoxidized polyunsaturated oil.

[0065] 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. Core-bark charge

[0066] Component A may further comprise a core-shell charge.

[0067] 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," it is understood 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.

[0068] 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 in accordance with ISO 11357-2, for example, with a heating rate of 20°C / min. Generally, the glass transition temperature of the core polymer is less than 10°C, preferably less than 0°C, and more preferably less than -20°C. Generally, the glass transition temperature of the shell polymer is greater than 60°C, preferably greater than 80°C, and more preferably greater than 100°C.

[0069] Unless otherwise indicated, the standards referred to throughout the application are those in force on the date of filing of the application.

[0070] The core polymer may comprise a polymer (homopolymer and / or copolymer) of a conjugated diene comprising 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) comprises from 1 to 12, preferably from 1 to 8, carbon atoms (such as butyl acrylate).

[0071] Advantageously, the core polymer comprises (or is essentially made up 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.

[0072] 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 in relation to the total weight of the core polymer, preferably less than 2% by weight, more preferably less than 1% by weight.

[0073] 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.

[0074] 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.

[0075] Advantageously, the bark 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.

[0076] In particular, the bark polymer comprises (or is essentially made up 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.

[0077] 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.

[0078] 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.

[0079] 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.

[0080] 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 motifs derived from methyl methacrylate relative to the total weight of said copolymer.

[0081] 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.

[0082] The bark polymer and / or the 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-1H-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 may 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 (e.g. C8-C12 cycloalkyl), and mixtures thereof.

[0083] 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.

[0084] According to one embodiment, the core-bark charge comprises:

[0085] - a core comprising (or essentially consisting of) a core polymer comprising (or consisting essentially of) a butadiene homopolymer and / or a butadiene-styrene copolymer,

[0086] - a bark comprising (or essentially consisting 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

[0087] - optionally one or more intermediate polymer layers, each layer comprising (or consisting essentially of) an intermediate polymer comprising (or consisting essentially of) a homopolymer of methyl methacrylate and / or copolymer of methyl methacrylate, in particular comprising at least 70% by weight of repeating motifs derived from methyl methacrylate relative to the total weight of said polymer.

[0088] The volume average diameter of the functionalized core-shell charge can be between 10 and 900 nm, preferably between 20 and 700 nm, more preferably between 20 and 500 nm. The volume average diameter can be measured by dynamic light scattering (DLS).

[0089] As an example of commercially available core-shell filler, we can cite the Clearstrength® (for example Clearstrength® XT100) or the Durastrength® marketed by Arkema, or the Paraloid™ (Paraloid™ 2650A, Paraloid™ 2691A) marketed by Dow.

[0090] The core-bark content can 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. Acrylic block copolymer

[0091] Component A may further comprise an acrylic block copolymer.

[0092] By "acrylic block copolymer" is meant a block copolymer comprising at least one acrylic block, that is to say, comprising at least one block made 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 R1 represents a hydrogen atom or a methyl radical, and -X- represents -O- or -NR11- with R11 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-.

[0093] By “block copolymer” is meant a copolymer comprising polymer blocks, that is to say polymer sequences chemically different from each other and linked together by a covalent bond.

[0094] 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.

[0095] 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 only 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 blocks A being obtained from identical or different monomers), more preferably a triblock copolymer ABA.

[0096] 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 mixture of monomers, more preferably at least 75% by weight.

[0097] 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, ...) are not taken into account.

[0098] 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.

[0099] 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).

[0100] Block B can 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.

[0101] Among acrylic block copolymers, we can cite for example the Nanostrength® marketed by Arkema (such as M52, M75, M65).

[0102] The total acrylic block copolymer content can be up to 30% by weight relative to the total weight of component A, preferably up to 20% by weight, more preferably up to 10% by weight. Other monofunctional (meth)acrylate monomer (M)

[0103] 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).

[0104] In this text, and unless otherwise stated (such as "exactly one"), "one" means one or more.

[0105] Advantageously, the monofunctional (meth)acrylate monomer (M) has the formula: CH2=C(Ra)-COORb, in which:

[0106] - Ra represents a hydrogen atom or a methyl group, preferably a methyl group,

[0107] - Rb represents an aliphatic or aromatic hydrocarbon group comprising optionally one or more groups chosen from ether, ester, hydroxyl, carbonyl, and mixtures thereof, preferably Rb represents an aliphatic or aromatic hydrocarbon group (not including a heteroatom), more preferably an alkyl group.

[0108] In the present text, "alkyl" means an acyclic or cyclic aliphatic hydrocarbon group (i.e., comprising an aliphatic ring), not comprising a carbon-carbon double bond.

[0109] When Rb represents an alkyl group, the monofunctional (meth)acrylate monomer (M) can be chosen from the C1-C22 alkyl (meth)acrylates, preferably the Cl-Cl2 alkyl (meth)acrylates.

[0110] In the present text, "alkyl (meth)acrylate in CX-CY" means an alkyl ester of (meth)acrylic acid in which the alkyl contains from X to Y carbon atoms.

[0111] In this text, "(meth)acrylic acid" means methacrylic acid or acrylic acid.

[0112] For example, the monofunctional (meth)acrylate monomer (M) can be selected 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, the tert-butylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate (CAS 7398-56-3), (octahydro-4,7-methano-1H-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.

[0113] 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 less than 90% by weight, more preferably at least 95% by weight, even more preferably at least 99% by weight, for example 100% by weight.

[0114] The total content of monofunctional (meth)acrylate monomer (M) can 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. Component A Additives

[0115] 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.

[0116] Advantageously, component A comprises a mixture of additives selected from adhesion promoters and rheological agents.

[0117] 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.

[0118] The crosslinking agent may 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.

[0119] The content of crosslinking agent may be up to 5% by weight relative to the total weight of component A.

[0120] The adhesion promoter can be selected from silanes (such as aminosilanes, epoxilanes, acryloyl silanes), phosphate ester-based adhesion promoters (such as mono-, di- and tri-phosphate esters of 2-hydroxyethyl (meth)acrylate), (meth)acrylic acid, (meth)acrylic acid amides (in particular 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 phosphate ester-based adhesion promoters of methacrylate, (meth)acrylic acid, and mixtures thereof, in particular a mixture of 2-hydroxyethyl methacrylate phosphate ester(s) and methacrylic acid.

[0121] The adhesion promoter content may be up to 5% by weight relative to the total weight of component A, preferably between 0.5% and 4% by weight.

[0122] The filler can be chosen from organic fillers, mineral fillers, and mixtures thereof.

[0123] As an example of mineral fillers, any mineral filler commonly used in adhesive compositions may be cited. These fillers typically take the form of particles of various geometries. They may, for example, be spherical, fibrous, or have an irregular shape.

[0124] The mineral filler can be chosen from clays (such as talc), quartz, carbonate fillers (in particular calcium carbonate, which can be coated with fatty acids (the latter preferably being precipitated)), kaolins, gypsum, hollow mineral microspheres (in particular hollow glass microspheres, such as those made of sodium and calcium borosilicate or aluminosilicate), zeolites, and mixtures thereof.

[0125] The mineral charge can be untreated or treated, for example with an organic acid including stearic acid.

[0126] 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.

[0127] In the present 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).

[0128] As an example of an organic filler, any organic filler, in particular polymeric, commonly used in the field of adhesive compositions may be cited.

[0129] 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.

[0130] The average particle size of the organic load may be less than or equal to 50 pm, preferably between 5 and 20 pm.

[0131] The filler content can be up to 10% by weight relative to the total weight of component A.

[0132] 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).

[0133] The thermal stabilizer content can be up to 3% by weight relative to the total weight of component A.

[0134] A UV stabilizer is typically introduced to prevent degradation resulting from a reaction with oxygen that is likely to form through the action of heat or light. UV stabilizers may include antioxidants capable of scavenging free radicals.

[0135] The UV stabilizer (or antioxidant) can be selected from among benzotriazoles, benzophenones, phosphites (such as tris(2,4-di-tert-butylphenyl)phosphite), so-called hindered phenols (such as ethylenebis(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(l-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(l,2,2,6,6-pentamethyl-4-piperidyl)sebacate (CAS No: 41556-26-7), methyl 1,2,2,6,6-pentamethyl-4-piperidylsebacate (CAS No: 82919-37-7), 4,4'-bis(a,a-dimethylbenzyl)diphenylamine), and mixtures thereof.

[0136] The UV stabilizer (or antioxidant) content can be up to 3% by weight relative to the total weight of component A.

[0137] The plasticizer can be any plasticizer commonly used in the field of adhesives.

[0138] 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, the Hydrogenated polyisoprene, and their mixtures.

[0139] The plasticizer content can be up to 8% by weight relative to the total weight of component A.

[0140] The rheological agent can be chosen from among thixotropic agents, for example from: - fumed silica (hydrophilic and / or hydrophobic), - urea derivatives resulting 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 - their mixtures.

[0141] By "waxes derived from castor oil" is meant waxes obtained from castor oil, in particular hydrogenated castor oil.

[0142] By "amide waxes" is meant waxes comprising one or more compounds having at least one amide group. In particular, amide waxes can be obtained from organic acid(s) (for example fatty acid(s)) and (di)amine(s).

[0143] 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.

[0144] Preferably, the rheological agent chosen from fumed silica, amide waxes, and mixtures thereof, in particular a mixture of hydrophobic fumed silica and amide wax.

[0145] 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.

[0146] The pigment can be selected from organic pigments, inorganic pigments, and mixtures thereof. For example, the pigment can be selected from phthalocyanine-based pigments (such as copper phthalocyanine, halogenated copper phthalocyanine, metal-free phthalocyanine), anthraquinone-based pigments (such as l-methylamino-4-o-tolylaminoanthraquinone, 1,4-diisopropyl aminoanthraquinone, 1,4-diaminoanthraquinone, 1,4-dibutyl-aminoanthraquinone, l-amino-4-anilinoanthraquinone), quinacridone-based pigments, perylene-based pigments, thioindigo-based pigments, quinophthalone-based pigments, titanium dioxide, carbon black, manganese ferrite, and mixtures thereof.

[0147] The pigment content can be up to 2% by weight relative to the total weight of component A.

[0148] The solvent can be any solvent suitable for acrylic adhesive compositions.

[0149] The solvent content can be up to 5% by weight relative to the total weight of component A. Organic peroxide

[0150] A peroxide is a compound comprising a single oxygen-oxygen bond.

[0151] The organic peroxide may be selected 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-butylperoxypentane), peracids (such as peracetic acid, perbenzoic acid), and mixtures thereof, preferably among the diacyl peroxides, for example dibenzoyl peroxide..

[0152] 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.

[0153] 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.

[0154] The weight ratio of tertiary aromatic amine / organic peroxide can be between 0.2 and 5, preferably between 0.3 and 2. Component B Additives

[0155] Component B may further comprise 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.

[0156] Advantageously, component B comprises a mixture of additives selected from plasticizers and rheological agents.

[0157] The total content of additives may be up to 90% by weight relative to the total weight of component B, preferably between 70% and 88% by weight.

[0158] 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.

[0159] The adhesion promoter may be selected from aminosilanes, epoxilanes, phosphate ester-based adhesion promoters (other than those comprising an acrylic group), and mixtures thereof.

[0160] The adhesion promoter content can be up to 5% by weight relative to the total weight of component B.

[0161] The filler can be chosen from organic fillers, mineral fillers, and mixtures thereof.

[0162] As an example of mineral fillers, any mineral filler commonly used in adhesive compositions may be cited. These fillers typically take the form of particles of various geometries. They may, for example, be spherical, fibrous, or have an irregular shape.

[0163] The mineral filler can be chosen from clays (such as talc), quartz, carbonate fillers (in particular calcium carbonate, which can be coated with fatty acids (the latter preferably being precipitated)), kaolins, gypsum, hollow mineral microspheres (in particular hollow glass microspheres, such as those made of sodium and calcium borosilicate or aluminosilicate), zeolites, and mixtures thereof.

[0164] The mineral charge can be untreated or treated, for example with an organic acid including stearic acid.

[0165] 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.

[0166] As an example of an organic filler, any organic filler, in particular polymeric, commonly used in the field of adhesive compositions may be cited.

[0167] 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.

[0168] The average particle size of the organic load may be less than or equal to 50 pm, preferably between 5 and 20 pm.

[0169] The filler content can be up to 10% by weight relative to the total weight of component B.

[0170] 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).

[0171] The thermal stabilizer content can be up to 1% by weight relative to the total weight of component B.

[0172] The UV stabilizer (or antioxidant) may be selected from 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.

[0173] The UV stabilizer (or antioxidant) content can be up to 1% by weight relative to the total weight of component B.

[0174] The plasticizer can be any plasticizer commonly used in the field of adhesives.

[0175] 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 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.

[0176] 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.

[0177] The rheological agent may be chosen from among thixotropic agents, for example from: - fumed silica (hydrophilic and / or hydrophobic), - urea derivatives resulting from the reaction of a diisocyanate monomer, preferably aromatic, such as diphenylmethylene diisocyanate (notably 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 - their mixtures.

[0178] 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.

[0179] Preferably, the rheological agent is chosen from among the amide waxes.

[0180] The content of rheological agent may be up to 10% by weight relative to the total weight of component B, preferably between 1% and 7% by weight.

[0181] The pigment may be selected from organic pigments, inorganic pigments, and mixtures thereof. For example, the pigment may be selected from phthalocyanine-based pigments (such as copper phthalocyanine, halogenated copper phthalocyanine, metal-free phthalocyanine), anthraquinone-based pigments (such as l-methylamino-4-o-tolylaminoanthraquinone, 1,4-diisopropyl aminoanthraquinone, 1,4-diaminoanthraquinone, 1,4-dibutyl-aminoanthraquinone, l-amino-4-anilinoanthraquinone), quinacridone-based pigments, perylene-based pigments, thioindigo-based pigments, quinophthalone-based pigments, titanium dioxide, carbon black, manganese ferrite, and mixtures thereof.

[0182] The pigment content can be up to 5% by weight relative to the total weight of component B.

[0183] The solvent can be any solvent suitable for acrylic adhesive compositions.

[0184] The solvent content can be up to 8% by weight relative to the total weight of component B.

[0185] Other characteristics of the two-component composition

[0186] Advantageously, the volume ratio of component A to component B is between 1 and 20, preferably between 5 and 15, for example about 10.

[0187] By "about X", we mean plus or minus 10% of the value of X.

[0188] According to one embodiment, the two-component composition according to the invention comprises:

[0189] - a component A comprising:

[0190] - between 20% and 80% by weight of benzyl methacrylate optionally alkoxylated,

[0191] - between 0.1% and 10% by weight of an organic zinc salt, the organic zinc salt preferably chosen from zinc carboxylates and mixtures thereof,

[0192] - between 0.1% and 7% by weight of a tertiary aromatic amine,

[0193] - between 5% and 40% by weight of a (meth)acrylate polymer,

[0194] - optionally between 5% and 30% by weight of core-bark filler,

[0195] - optionally up to 20% by weight of acrylic block copolymer,

[0196] - optionally up to 15% by weight of a (meth)acrylate monomer monofunctional (M) different from optionally alkoxylated benzyl methacrylate, and

[0197] - optionally up to 30% by weight of one or more additives selected from the 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,

[0198] relative to the total weight of component A, and

[0199] - a component B comprising:

[0200] - between 10% and 40% by weight of an organic peroxide, and

[0201] - up to 90% by weight of one or more additives selected from the promoters adhesion, fillers (other than a core-bark filler), thermal stabilizers, UV stabilizers (or antioxidants), plasticizers, rheological agents, pigments, solvents, and mixtures thereof,

[0202] relative to the total weight of component B,

[0203] the volume ratio of component A relative to component B being between 1 and 20.

[0204] 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.

[0205] The ingredients of this embodiment and their particular contents are as described above, including preferred embodiments and features.

[0206] In particular, the two-component composition according to the invention comprises:

[0207] - a component A comprising:

[0208] - between 40% and 60% by weight of benzyl methacrylate optionally alkoxylated, preferably non-alkoxylated

[0209] - between 0.5% and 3% by weight of an organic zinc salt, the organic zinc salt being preferably chosen from zinc acrylate, zinc methacrylate, zinc acetate, zinc propionate, and mixtures thereof,

[0210] - between 0.1% and 7% by weight of a tertiary aromatic amine, the aromatic amine tertiary is preferably chosen from alkoxylated p-toluidines, alkoxylated anilines, and mixtures thereof,

[0211] - between 15% and 30% by weight of a (meth)acrylate polymer, the polymer (meth)acrylate being preferably selected from urethane (meth)acrylate polymers,

[0212] - optionally between 10% and 22% by weight of core-shell filler,

[0213] - optionally up to 10% by weight of acrylic block copolymer,

[0214] - optionally up to 3% by weight of a (meth)acrylate monomer monofunctional (M) different from optionally alkoxylated benzyl methacrylate, and

[0215] - 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,

[0216] in relation to the total weight of component A, and

[0217] - a component B comprising:

[0218] - between 12% and 30% by weight of an organic peroxide, the organic peroxide being preferably chosen from among the diacyl peroxides, and

[0219] - between 70% and 88% by weight of one or more additives selected from the promoters adhesion, 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 selected from the plasticizers and rheological agents,

[0220] relative to the total weight of component B,

[0221] the volume ratio of component A to component B being between 5 and 15.

[0222] 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 features.

[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. Use of the two-component composition

[0227] 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.

[0228] The two-component composition according to the invention is as described above, including preferred embodiments and features. Substrate assembly process

[0229] The present invention also relates to a method for assembling substrates comprising:

[0230] - coating, on at least one surface of the substrates to be assembled, the composition two-component according to the invention as described above (including preferred embodiments and features), then

[0231] - bringing the substrates into contact, then

[0232] - crosslinking of the composition.

[0233] The two-component composition according to the invention is as described above, including preferred embodiments and features.

[0234] It is understood that, during the coating step and the contacting step, the two-component composition according to the invention is in the non-crosslinked state.

[0235] The crosslinking step can be carried out at a temperature between 10°C and 40°C, preferably between 15°C and 30°C, in particular at room temperature (for example between 18°C ​​and 25°C).

[0236] The substrates may be identical or different.

[0237] A wide variety of substrates can be used. They can, for example, be plastic, glass, metal and / or composite. Preferably, at least one substrate is plastic, and more preferably, all substrates are plastics.

[0238] The plastic may be PVC, polycarbonate, polymethyl methacrylate (PMMA), polystyrene and / or acrylonitrile butadiene styrene (ABS), preferably polycarbonate and / or ABS, in particular polycarbonate.

[0239] The metal may be pure or an alloy, for example aluminium and / or steel (including stainless steel and / or galvanized steel).

[0240] The composite may be a reinforced plastic material, such as a fiber-reinforced plastic, in particular a sheet-molded composite (SMC). The fibers of the fiber-reinforced plastic may be glass, carbon, aramid, or basalt fibers, preferably glass fibers. The fiber length may vary from 6 mm to 50 mm. The polymer in the reinforced plastic material may be a polyester, polyolefin, epoxy, or vinyl ester resin. The polymer in the reinforced plastic material is preferably unsaturated. The reinforced plastic material may comprise other compounds besides the fibers and the polymer (such as filler and / or catalyst). Article

[0241] 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.

[0242] The article can be obtained by means of the substrate assembly process according to the invention (including preferred embodiments and features).

[0243] 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.

[0244] For example, the article may be a part of an electronic object (computer, telephone, television, ...).

[0245] All the embodiments described above can be combined with each other. In particular, the various aforementioned constituents of the composition, and especially the preferred embodiments, can be combined with each other.

[0246] The examples below are given purely for illustrative purposes of the invention and should not be interpreted as limiting its scope. Examples Example 1#: Ingredients and Measurement Methods Ingredients Used

[0247] The following ingredients were used:

[0248] - VISIOMER® BNMA (by Evonik): benzyl methacrylate,

[0249] - MERACRYL® HEMA 98 (by Rohm): 2-hydroxyethyl methacrylate,

[0250] - VISIOMER® GLYFOMA (by Evonik): glycerol methacrylate form (mixture of isomers, CAS: 1620329-57-8),

[0251] - Oligomer: dimethacrylate urethane 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,

[0252] - Bisomer® PTE (by Geo Specialty Chemicals): mixture of para-toluidines ethoxylated (CAS: 103671-44-9), tertiary aromatic amine,

[0253] - Clearstrength® XT 100 (by Arkema): core-bark charge,

[0254] - Methacrylic acid (by Sigma-Aldrich),

[0255] - SR9054 (by SARTOMER): methacrylate mixture comprising functional groups phosphate, adhesion promoter,

[0256] - AEROSIL® R 202 (by Evonik): hydrophobic pyrogenated silica (treated with dimethyl polysiloxane), rheological agent,

[0257] - CRAYVALLAC® SLT (by Arkema): micronized amide wax, agent rheological,

[0258] - DYMALINK® 708 (by Cray Valley, a Total company): zinc methacrylate (CAS: 13189-00-9), organic zinc salt,

[0259] - Zinc acetate (by Sigma-Aldrich): CAS: 557-34-6, organic zinc salt,

[0260] - PEROXAN BP-Paste 50 PF 1 (by PERGAN): dibenzoyl peroxide paste 50%, organic peroxide,

[0261] - Vikoflex® 7170 (by Cargill): epoxy soybean oil (CAS: 8013-07-8), plasticizer. Measurement methods

[0262] The shear strength (denoted LSS for Lap Shear Strength) was measured according to ISO 4587 (2003). A 250 µm layer of the composition to be tested was applied between two polycarbonate sheets, each sheet being 2 mm thick. The shear strength was measured at 23°C, after 24 hours of curing at 23°C and 50% humidity, and the fracture surface was noted (a semi-cohesive and semi-adhesive fracture was noted as RSC). The shear stress was applied using a tensile testing machine at a constant speed of 5 mm / min.

[0263] 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 deposited in a perforated container, and the temperature probe was placed to monitor the exothermic reaction and record the temperature as a function of time. At the end of the test, the exothermic peak was determined to be the maximum observed temperature.

[0264] 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.

[0265] The odor of the compositions was evaluated on component A in a blind test 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).

[0266] Example 2: Preparation of compositions according to the invention and comparative compositions

[0267] Compositions 1-7 were obtained by introducing a component 1A-7A and a component B into a twin cartridge (protected from air and moisture), and then mixing them using a static mixer attached to the end of the twin cartridge, at room temperature (23 °C) with a volume ratio A / B of 10. The component A used for 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: 29% of PEROXAN BP-Paste 50 PF 1, - 66% of Vikoflex® 7170, and 5% of CRAYVALLAC ® SLT,

[0268] the percentages being percentages by weight relative to the total weight of component B.

[0269] Components A and B were prepared separately by mixing their ingredients by centrifugation until homogenized (SpeedMixer™ mixer).

[0270] [Tables 1] Ingredient IA (co mp) 2A (inv ) 3A (inv ) 4A (co mp) 5A (co mp) 6A (co mp) 7A (co mp) VISIOMER® BN MA 50.8 50.2 50.2 - - - - MERACRYL® HE MA 98 - - - 43.6 45.7 - - VISIOMER® GLY FOMA - - - - - 50.8 50.2 Oligomer 23 22.8 22.8 30 28 23 22.8 Bisomer® PTE 1 1 1 1 1 1 1 Clearstrength® XT 100 17 16.8 16.8 17 17 17 16.8 Methacrylic acid 1 1 1 1 1 1 1 SR9054 1.1 1.1 1.1 1.1 1.1 1.1 1.1 AEROSIL® R 202 3.6 3.6 3.6 3.3 3.2 3.6 3.6 CRAYVALLAC® SLT 2.5 2.5 2.5 2.5 2.5 2.5 2.5 DYMALINK® 70 8 - 1 - 0.5 - - 1 Zinc acetate - - 1 - 0.5 - -

[0271] Example 3: Properties of the compositions prepared in Example 2

[0272] 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.

[0273] [Tables2] Property 1 (comp) 2 (inv) 3 (inv) 4 (comp) 5 (comp) 6 (comp) 7 (comp) LSS (MPa) 5.8 7.1 8.6 0 0 0 6.6 Facies RSC RSC RSC NA NA NA RSC Time π c (min) 38 8.5 8.5 14 13 15 8 Properties after aging LSS (MPa) 1.8 8.6 7.7 ND ND ND manual Facies RSC RSC RSC ND ND ND ND Time π c (min) 41 8.5 8.5 ND ND ND ND

[0274] NA: not applicable, ND: not determined, manual: peels off by hand

[0275] Compositions 1 to 7 are all compositions with a low odor (score less than 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 greater than 3).

[0276] 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. Indeed, the peak time is reduced from about forty minutes for the comparative composition 1 (without organic zinc salt) to less than 10 minutes for compositions 1 and 2 according to the invention.

[0277] Moreover, unlike comparative composition 1, compositions 2 and 3 according to the invention retain high shear strength values ​​on polycarbonate, even after aging.

[0278] However, comparative compositions 4 and 5 based on 2-hydroxyethyl methacrylate (MERACRYL® HEM A 98, a low-odor monomer) have 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 methacrylate (VISIOMER® GLYFOMA, a 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 separates by hand after aging. Comparative composition 7 is therefore not stable during storage because the adhesion does not persist over time.

[0279] 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, rapidly crosslinking, and have high adhesion to polycarbonate even after aging.

Claims

Demands

1. 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.

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

3. A 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. Method for assembling substrates 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 - crosslinking 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.