Two-component composition

Abstract

The invention relates to a two-component composition comprising: - a component A comprising: - a monofunctional (meth)acrylate monomer, and - a urethane (meth)acrylate polymer obtained without the use of isocyanate by means of a method comprising polycondensation by transurethanisation followed by a step of (meth)acrylate functionalisation, and - a component B comprising: - an initiator. 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, the composition binding at least two substrates of the 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 typically crosslink by radical polymerization. Most acrylic systems are two-component systems. The first component usually comprises the reactive monomers, and the second component is the initiator.

[0006] The first component may also include a urethane (meth)acrylate polymer, classically obtained by reaction between a polyol and a polyisocyanate, thus forming one or more urethane (-OC(=O)-NH-) bonds, followed by functionalization with a (meth)acrylate.

[0007] However, polyisocyanates are toxic (causing symptoms such as allergies, asthma, or breathing difficulties), and their handling and use require specific and strict precautions to protect human health and the environment in general. Furthermore, there is a European REACH regulation limiting the content of free diisocyanates (for example, residual diisocyanates contained in a conventionally produced urethane (meth)acrylate polymer) to less than 0.1% by weight in the final compositions.

[0008] Thus, the present invention aims to provide a two-component composition whose preparation does not require the use of isocyanate, and which has mechanical properties that allow, in particular, its use as a structural adhesive. Furthermore, it is preferable that the two-component composition does not yellow, or only minimally, over time.

[0009] Summary of the invention

[0010] The present invention relates to a two-component composition comprising:

[0011] - a component A comprising:

[0012] - a monofunctional (meth)acrylate monomer, and

[0013] - a urethane (meth)acrylate polymer obtained without the use of isocyanate by a process comprising transurethanation polycondensation followed by a (meth)acrylate functionalization step, and

[0014] - a component B comprising:

[0015] - a primer.

[0016] 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.

[0017] The present invention also relates to a method for assembling substrates comprising:

[0018] - coating, on at least one surface of the substrates to be assembled, with the two-component composition according to the invention, then

[0019] - bringing the substrates into contact, then

[0020] - cross-linking of the composition.

[0021] 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.

[0022] The present invention makes it possible to meet the needs mentioned above. In particular, the two-component composition according to the invention has mechanical properties (in particular shear strength) maintained or improved compared to a two-component composition comprising a conventionally obtained (meth)acrylate urethane polymer (involving a reaction between a polyol and a polyisocyanate).

[0023] Description of the invention

[0024] 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 the monofunctional (meth)acrylate monomer), while a second part, in this case component B, comprises the initiator of the polymerization reaction. The initiation of the polymerization reaction can therefore only occur when component A comes into contact with component B.

[0025] Monofunctional (meth)acrylate monomer

[0026] Component A comprises a monofunctional (meth)acrylate monomer (preferably a monofunctional methacrylate monomer), that is, a monomer comprising exactly one (meth)acrylate group. In this text, and unless otherwise stated (such as "exactly one"), "one" means one or more.

[0027] In this text, "(meth)acrylate" means methacrylate or acrylate.

[0028] Advantageously, the monofunctional (meth)acrylate monomer has the formula (I): CH2=C(R a )-COOR b , in which:

[0029] - R a represents a hydrogen atom or a methyl group, preferably a methyl group,

[0030] - 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 hydrocarbon group possibly comprising one or more groups selected from ether, ester, hydroxyl, carbonyl, and mixtures thereof, more preferably an aliphatic hydrocarbon group comprising one or more hydroxyl groups.

[0031] The various groups, radicals and letters which are included in the formulas described in this text retain, throughout this text, and in the absence of any indication to the contrary, the same definition.

[0032] The monofunctional (meth)acrylate monomer can be a C1-C22 (meth)acrylate, preferably a C1-C15, more preferably a C1-C4.

[0033] In this text, "CX-CY (meth)acrylate" means a (meth)acrylic acid ester comprising X to Y carbon atoms, excluding carbon atoms originating from (meth)acrylic acid. For example, when the monofunctional (meth)acrylate monomer has formula (I), a C4 (meth)acrylate means that R b comprises 4 carbon atoms.

[0034] In this text, "(meth)acrylic acid" means methacrylic acid or acrylic acid.

[0035] For example, the monofunctional (meth)acrylate monomer can be chosen from methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (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-1 H-indenyl)methyl (meth)acrylate (CAS 127823-21-6), benzyl (meth)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.

[0036] Preferably, the monofunctional (meth)acrylate monomer is selected from methyl (meth)acrylate, tert-butyl (meth)acrylate, 2-octyl (meth)acrylate, isobornyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, (octahydro-4,7-methano-1 H-indenyl)methyl (meth)acrylate, benzyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and mixtures thereof.

[0037] More preferably, the monofunctional (meth)acrylate monomer is chosen from methyl methacrylate, tert-butyl methacrylate, 2-octyl methacrylate, isobornyl methacrylate, 3,3,5-trimethylcyclohexyl methacrylate, tert-butylcyclohexyl methacrylate, (octahydro-4,7-methano-1 H-indenyl)methyl methacrylate, benzyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, and mixtures thereof, in particular hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, and mixtures thereof, for example hydroxyethyl methacrylate.

[0038] The total content of monofunctional (meth)acrylate monomer 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.

[0039] 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%.

[0040] Urethane (meth)acrylate polymer

[0041] Component A comprises a urethane (meth)acrylate polymer, preferably a urethane (meth)acrylate oligomer, obtained without the use of isocyanate by a process comprising transurethanization polycondensation. Preferably, the urethane (meth)acrylate polymer is a urethane methacrylate polymer.

[0042] The term "isocyanate" refers to a compound containing one or more isocyanate groups (-N=C=O). The term "oligomer" is familiar to those skilled in the art and can be defined as a small polymer, for example, comprising 2 to 30 repeating units.

[0043] Advantageously, the urethane (meth)acrylate polymer has zero isocyanate monomer content. The isocyanate monomer content can be measured by high-performance liquid chromatography coupled with an ultraviolet detector (HPLC-UV). For example, the isocyanate monomer content can be measured using the following method: urea derivatives are obtained by reacting the isocyanate group NCO with an amine (1-(2-methoxyphenyl)piperazine or PPZ), by diluting / solubilizing the sample with a tetrahydrofuran solution containing 0.012 g / mL PPZ. The PPZ derivatives formed from the isocyanates contained in the sample to be analyzed are then quantified by a reverse phase HPLC system with a C18 stationary phase with a mobile phase gradient comprising a part of water acidified with acetic acid and buffered with sodium acetate to reach a pH of about 4.5, and a part of tetrahydrofuran.Detection is performed using a UV detector operating at 254 nm. These compounds are identified and quantified by comparing their retention time and chromatographic peak area with those of standard PPZ derivatives obtained by reaction of a diisocyanate monomer of known nature and concentration.

[0044] Advantageously, the urethane (meth)acrylate polymer comprises between two and six (meth)acrylate groups, preferably exactly two (meth)acrylate groups. Preferably, the urethane (meth)acrylate polymer is a urethane methacrylate polymer.

[0045] The urethane (meth)acrylate polymer can have a number average molecular weight between 500 g / mol and 20000 g / mol, preferably between 700 g / mol and 10000 g / mol, for example between 800 g / mol and 6500 g / mol.

[0046] In this text, the number-average molecular weight can be determined by size-exclusion chromatography (SEC), for example using polystyrene reference standards and tetrahydrofuran as solvent.

[0047] The total urethane (meth)acrylate polymer content may be between 5% and 45% by weight relative to the total weight of component A, preferably between 10% and 40% by weight, more preferably between 15% and 40% by weight.

[0048] Transurethanation occurs when a first alcohol reacts with a first carbamate group (also called urethane) to form a second carbamate group and a second alcohol. For example, transurethanation involving the alcohol R1-OH and the carbamate group R-NH-C(=O)-O-R2 results in the carbamate group R-NH-C(=O)-O-Ri and the alcohol R2-OH. For polycondensation to occur, transurethanation is carried out with a polycarbamate and a polyol.

[0049] Advantageously, polycondensation by transurethanization is carried out from a reaction medium comprising a polycarbamate and a polyol polymer, preferably a dicarbamate and a diol polymer.

[0050] • Polycarbamate

[0051] Polycarbamate is preferably a dicarbamate.

[0052] Polycarbamate can be aliphatic or aromatic, preferably aliphatic.

[0053] Advantageously, the polycarbamate is obtained from a reaction medium comprising a primary diamine, preferably aliphatic, and an organocarbonate, preferably aliphatic, the organocarbonate not comprising a carbonate group involved in a ring. Preferably, the reaction medium further comprises a catalyst.

[0054] By "primary diamine" we mean a compound comprising exactly two primary amine groups (-NH2).

[0055] The primary diamine can be selected from ethylenediamine, propylenediamine (e.g., 1,3-), butylenediamine (e.g., 1,4-), pentamethylenediamine (e.g., 1,5-), hexamethylenediamine (e.g., 1,6-), heptanediamine (e.g., 1,7-), octanediamine (e.g., 1,8-), nonanediamine (e.g., 1,9-), decanediamine (e.g., 1,10-), undecanediamine (e.g., 1,11-), dodecanediamine (e.g., 1,12-), isophoronediamine, 4-methylcyclohexane-1,3-diamine, 2-methylcyclohexane-1,3-diamine, 1,2- and / or 1,4-cyclohexanediamine, 4,4'- and / or 2,4'-methylenebis(cyclohexylamine), 2,4- and / or 2,6-diaminotoluene, 4,4'- and / or 2,4'-diaminodiphenylmethane, m-xylylenediamine, hydrogenated m-xylylenediamine, tetramethylxylenediamine, 2,4,6-trimethyl-1,3-phenylenediamine, naphthalene-1,8-diamine, dimeric diamines, polyetherdiamines, and mixtures thereof.

[0056] Dimeric diamines can be obtained by fatty acid dimerization followed by an amination reaction (to convert the carboxylic acid groups into a primary amine). Preferably, the dimeric diamine comprises between 32 and 48 carbon atoms, preferably between 34 and 40 carbon atoms, for example, 36 carbon atoms (CAS: 68955-56-6). Dimeric diamines may be commercially available, for example, under the trade name Priamine™ (by Cargill).

[0057] A polyetheramine can be defined as an amine containing at least two ether groups (identical or different). Polyetherdiamines may contain ethoxy (-OCH2CH2-), propoxy (e.g., -OCH2CH(CH3)-), and / or butoxy (e.g., -OCH2CH(CH2CH3)-) groups. Examples of polyetherdiamines include O,O'-bis(2-aminopropyl) polypropylene glycol-block-polyethylene glycol-block-polypropylene glycol (CAS: 65605-36-9) and / or poly(propylene glycol) bis(2-aminopropyl ether) (CAS: 9046-10-0). Polyetheramines are commercially available, for example, under the trade name Jeffamine® (by HUNTSMAN).

[0058] Preferably, the primary diamine is selected from ethylene diamine, propylene diamine, butylene diamine, pentamethylene diamine, hexamethylene diamine, heptanediamine, octanediamine, nonanediamine, decanediamine, undecanediamine, dodecanediamine, isophorone diamine, 4-methylcyclohexane-1,3-diamine, 2-methylcyclohexane-1,3-diamine, 1,2- and / or 1,4-cyclohexanediamine, 4,4'- and / or 2,4'-methylenebis(cyclohexylamine), hydrogenated m-xylylenediamine, dimeric diamines, polyetherdiamines, and mixtures thereof.

[0059] Preferably, the primary diamine is chosen from isophorone diamine, 4-methylcyclohexane-1,3-diamine, 2-methylcyclohexane-1,3-diamine, 1,2- and / or 1,4-cyclohexanediamine, 4,4'- and / or 2,4'-methylenebis(cyclohexylamine), hydrogenated m-xylylenediamine, dimeric diamines, and mixtures thereof, in particular dimeric diamines.

[0060] Primary diamine may have a molar mass between 60 g / mol and 5000 g / mol, preferably between 100 g / mol and 1000 g / mol, and more preferably between 100 g / mol and 700 g / mol. In particular, primary diamine may have a molar mass between 300 g / mol and 5000 g / mol, preferably between 300 g / mol and 1000 g / mol, and more preferably between 300 g / mol and 700 g / mol.

[0061] By "organocarbonate" we mean a compound comprising a carbonate ester group (-OC(=O)-O-), preferably exactly a carbonate ester group (i.e. an organomonocarbonate).

[0062] Advantageously, the organocarbonate is chosen from C1-C4 dialkyl carbonates (preferably linear), diphenyl carbonate, and mixtures thereof, preferably from C1-C4 dialkyl carbonates and mixtures thereof, and more preferably from dimethyl carbonate, diethyl carbonate, and mixtures thereof. A "C1-C4 dialkyl carbonate" is understood to be a carbonate ester functionalized by two alkyl groups in which the number of carbon atoms varies independently from 1 to 4. For example, dimethyl carbonate is a C1 dialkyl carbonate.

[0063] 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.

[0064] The carbonate / primary diamine molar ratio may be greater than or equal to 2, preferably greater than or equal to 5, more preferably greater than or equal to 8. For example, said molar ratio may be between 2 and 25, preferably between 5 and 20, more preferably between 8 and 15.

[0065] The catalyst can be any catalyst commonly used to catalyze the reaction between a primary amine and an organocarbonate. For example, the catalyst can be chosen from Lewis bases, Brønstedt bases (preferably those whose conjugate acids have a pKa greater than or equal to 10), and mixtures thereof.

[0066] The Brønstedt base can, for example, be chosen from carbonates (such as CaCCh, Na2COs and / or K2CO3), alkali metal hydroxides (such as NaOH and / or KOH), alkali metal alkoxides (such as sodium methoxide, potassium methoxide, sodium ethoxide and / or potassium tert-butanolate), and mixtures thereof.

[0067] The Lewis base can, for example, be chosen from among alicyclic tertiary amines (such as N,N-dicyclohexylmethylamine, 1,4-diazabicyclo[2.2.2]octane (DABCO) and / or 2,2'-diethyl ether (DMDEE)), acyclic tertiary amines (such as triethylamine, tripropylamine, tributylamine, trihexylamine, N-methyldiethanolamine, N-methyldiisopropylamine and / or N-butyldiethanolamine), amidines (such as 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) and / or 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU)), guanidines (such as N,N,N',N'-tetramethylguanidine, 1 ,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) and / or N-methyl triazabicyclodecene (Me-TBD), phosphazenes (such as 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphoride (BMEP)), organophosphanes (such as tributylphosphane, triphenylphosphane, tris-p-tolylphosphane, methyldiphenylphosphane), and mixtures thereof.

[0068] Preferably, the Lewis base is chosen from alicyclic tertiary amines, acyclic tertiary amines, amidines, guanidines, and mixtures thereof, more preferably from alicyclic tertiary amines, amidines, guanidines, and mixtures thereof, especially from guanidines.

[0069] The catalyst / primary diamine molar ratio can be between 0.01 and 1, preferably between 0.03 and 0.5, more preferably between 0.05 and 0.3.

[0070] According to one embodiment, the polycarbamate is an aliphatic dicarbamate obtained from a reaction medium comprising an aliphatic primary diamine, an aliphatic organomonocarbonate and a catalyst.

[0071] Advantageously, the reaction medium consists essentially of the ingredients mentioned above. By "consists essentially" is meant that the reaction medium comprises less than 5% by weight of ingredients other than the aforementioned ingredients, relative to the total weight of the reaction medium, preferably less than 2% by weight, and even more preferably less than 1% by weight.

[0072] The ingredients of this embodiment are as described above, including preferred embodiments and characteristics (in particular molar ratios).

[0073] Preferably, said reaction medium comprises (advantageously, is essentially made up of):

[0074] - a primary diamine selected from ethylenediamine, propylenediamine, butylenediamine, pentamethylenediamine, hexamethylenediamine, heptanediamine, octanediamine, nonanediamine, decanediamine, undecanediamine, dodecanediamine, isophoronediamine, 4-methylcyclohexane-1,3-diamine, 2-methylcyclohexane-1,3-diamine, 1,2- and / or 1,4-cyclohexanediamine, 4,4'- and / or 2,4'-methylenebis(cyclohexylamine), hydrogenated m-xylylenediamine, dimeric diamines, polyetherdiamines, and mixtures thereof,

[0075] - an organocarbonate selected from C1-C4 dialkyl carbonates and mixtures thereof, and

[0076] - a catalyst selected from alicyclic tertiary amines, acyclic tertiary amines, amidines, guanidines, and mixtures thereof.

[0077] The ingredients of this embodiment are as described above, including preferred embodiments and characteristics (in particular molar ratios).

[0078] The reaction to obtain polycarbamate can be carried out at a temperature between 40°C and 120°C, preferably between 60°C and 100°C. The reaction to obtain polycarbamate can be carried out at atmospheric pressure.

[0079] • Polyol polymer

[0080] The polyol polymer is preferably a diol polymer.

[0081] The polyol polymer can be aliphatic or aromatic, preferably aliphatic.

[0082] The polyol polymer can have a number average molecular weight between 100 g / mol and 5000 g / mol, preferably between 200 g / mol and 3000 g / mol, for example between 400 g / mol and 2000 g / mol.

[0083] The polyol polymer can be a polyether polyol, a polycarbonate polyol and / or a polyester polyol, preferably a polyether polyol.

[0084] Preferably, the polyether polyol is a polyether diol, in particular selected from polyethylene glycol, polypropylene glycol, poly(tetrahydrofuran), and mixtures thereof, in particular poly(tetrahydrofuran).

[0085] Polycarbonate polyol is preferably a polycarbonate diol, the diol being able to comprise between 2 and 10 carbon atoms. For example, the diol can be a linear diol comprising between 4 and 8 carbon atoms (such as 1,6-hexanediol) and / or a 2,2-dialkyl-1,3-propanediol (such as neopentyl glycol).

[0086] Polyester polyol is preferably a polyester diol, which can be obtained by the reaction between a dicarboxylic acid and a diol. The dicarboxylic acid can have between 4 and 12 carbon atoms and is preferably linear (such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and / or 1,12-dodecanedioic acid). The diol can have between 2 and 10 carbon atoms and can, for example, be a linear diol with between 4 and 8 carbon atoms (such as 1,6-hexanediol) and / or a 2,2-dialkyl-1,3-propanediol (such as neopentyl glycol).

[0087] • Other characteristics of polycondensation by transurethanation

[0088] A polyol-type chain extender can potentially be implemented during polycondensation by transurethanization.

[0089] By "polyol-type chain extender" we mean a compound comprising at least two hydroxyl groups and not being a polymer.

[0090] The chain extender may have a molar mass between 50 g / mol and 300 g / mol, preferably between 60 g / mol and 200 g / mol. The chain extender may be selected from 1,4-butanediol, ethylene glycol, 1,6-hexanediol, 1,2,3-propanetriol, trimethylolethane, trimethylolpropane, 1,2,6-hexanetriol, triethanolamine, and mixtures thereof.

[0091] The chain extender / polyol polymer molar ratio can go up to 0.1.

[0092] Advantageously, the polycarbamate / polyol molar ratio (including the polyol polymer(s) and any chain extender) is chosen so as to obtain a urethane polymer terminated by hydroxyl groups (i.e., hydroxyl groups are present at each end of the polymer chain).

[0093] Preferably, the reaction medium for implementing polycondensation by transurethanization also includes a catalyst.

[0094] The catalyst can be chosen from organic derivatives of transition metals (especially titanium and / or zirconium), organic derivatives of post-transition metals (especially bismuth, zinc and / or tin), organic derivatives of alkali metals (especially sodium and / or potassium), carbonates (such as CaCCh, Na2COs and / or K2CO3), alkali metal hydroxides (such as NaOH and / or KOH), Lewis bases, and mixtures thereof.

[0095] Examples of organic derivatives of transition metals are acetyl acetonate, titanium and / or zirconium tetrapropylate and / or tetrabutylate.

[0096] Examples of organic derivatives of post-transition metals include neodecanoate, bismuth and / or zinc, and dibutyltin and / or dioctyltin dilaurate.

[0097] Examples of organic derivatives of alkali metals are alkali metal alkoxides such as sodium methoxide, potassium methoxide, sodium ethoxide and / or potassium tert-butanolate.

[0098] Examples of Lewis bases include alicyclic tertiary amines (such as N,N-dicyclohexylmethylamine, 1,4-diazabicyclo[2.2.2]octane (DABCO), and / or 2,2'-diethyl ether (DMDEE)), acyclic tertiary amines (such as triethylamine, tripropylamine, tributylamine, trihexylamine, N-methyldiethanolamine, N-methyldiisopropylamine, and / or N-butyldiethanolamine), amidines (such as 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) and / or 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU)), and guanidines (such as N,N,N',N'-tetramethylguanidine, 1 ,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) and / or N-methyl triazabicyclodecene (Me-TBD), phosphazenes (such as 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphoride (BMEP)) and / or organophosphanes (such as tributylphosphane, triphenylphosphane, tris-p-tolylphosphane, methyldiphenylphosphane).Preferably, the catalyst is chosen from organic derivatives (especially alkoxides) of alkali metals, alkali metal hydroxides, and mixtures thereof.

[0099] More preferably, the catalyst is chosen from sodium alkoxides, potassium alkoxides, sodium hydroxide, potassium hydroxide, and mixtures thereof, even more preferably from sodium alkoxides, potassium alkoxides, and mixtures thereof, in particular from sodium methoxide, potassium methoxide, sodium ethoxide, potassium tert-butanolate, and mixtures thereof.

[0100] The catalyst / polycarbamate molar ratio can be between 0.01 and 1, preferably between 0.03 and 0.5, more preferably between 0.05 and 0.3.

[0101] According to one embodiment, polycondensation by transurethanization is carried out from a reaction medium comprising an aliphatic dicarbamate, an aliphatic diol polymer and a catalyst.

[0102] Advantageously, the reaction medium for polycondensation by transurethanation consists essentially of the ingredients mentioned above. By "consists essentially of" is meant that the reaction medium comprises less than 5% by weight of ingredients other than the aforementioned ingredients, relative to the total weight of the reaction medium, preferably less than 2% by weight, and even more preferably less than 1% by weight.

[0103] The ingredients of this embodiment (including the characteristics of the reaction for obtaining the polycarbamate) are as described above, including preferred embodiments and characteristics (in particular molar ratios).

[0104] Preferably, said reaction medium comprises (advantageously, is essentially made up of):

[0105] - an aliphatic dicarbamate obtained from a reaction medium comprising an aliphatic primary diamine, an aliphatic organomonocarbonate and a catalyst,

[0106] - a polyether diol, and

[0107] - a catalyst chosen from organic derivatives of alkali metals, alkali metal hydroxides, and mixtures thereof.

[0108] The ingredients of this embodiment (including the characteristics of the reaction for obtaining the polycarbamate) are as described above, including preferred embodiments and characteristics (in particular molar ratios).

[0109] Polycondensation by transurethanization can be carried out at a temperature between 50°C and 190°C, preferably between 100°C and 180°C. Polycondensation by transurethanization can be carried out at a pressure lower than atmospheric pressure (e.g., less than 100 kPa, preferably less than 50 kPa) for at least part of the polycondensation (e.g., for at least 2 hours, preferably between 3 and 8 hours).

[0110] • Functionalization (meth)acrylate

[0111] The process for obtaining the urethane (meth)acrylate polymer also includes a functionalization step (meth)acrylate (preferably methacrylate), after polycondensation by transurethanization.

[0112] The (meth)acrylate functionalization step allows the introduction of one or more (meth)acrylate groups, notably by reacting the hydroxyl groups present at the end of the chain of the urethane polymer obtained at the end of the polycondensation by transurethanization.

[0113] The (meth)acrylate functionalization step can be implemented with a (meth)acrylate precursor such as a (meth)acryloyl halide (preferably chloride and / or bromide), (meth)acrylic anhydride and / or (meth)acrylic acid, preferably with (meth)acryloyl chloride, (meth)acryloyl bromide and / or (meth)acrylic anhydride, more preferably with methacryloyl chloride, methacryloyl bromide and / or methacrylic anhydride.

[0114] The precursor (meth)acrylate / urethane polymer molar ratio may be greater than or equal to 2, preferably greater than or equal to 3. For example, said molar ratio may be between 2 and 10, preferably between 3 and 6.

[0115] Primer

[0116] Component B comprises an initiator, preferably a radical initiator, i.e., an initiator that generates radicals. For example, the radicals can be generated by a redox reaction and / or by exposure to electromagnetic radiation (when a photoinitiator is used), preferably by a redox reaction.

[0117] Suitable radical initiators are well known to those skilled in the art and can be chosen in particular from among peroxides (i.e. comprising a single oxygen-oxygen bond), azo initiators, photoinitiators, and mixtures thereof, preferably from among peroxides and mixtures thereof, more preferably from among organic peroxides and mixtures thereof. The peroxide can be chosen from inorganic persulfate compounds (such as ammonium persulfate, potassium persulfate, sodium persulfate), hydrogen peroxide, organic hydroperoxides (such as cumene hydroperoxide, β-butyl hydroperoxide, β-menthane hydroperoxide, methyl ethyl ketone peroxide), peroxyesters (such as β-butyl peroxyneodecanoate, β-butyl peroxybenzoate, β-butyl peroxyisobutyrate, β-amyl peroxypivalate, β-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.

[0118] When a peroxide is used as a radical initiator, the composition according to the invention may further comprise a reducing agent (used to promote the decomposition of the peroxide), introduced into component A. Suitable reducing agents may be selected from tertiary amines, alpha-aminosulfones (such as bis(tolylsulfonymethyl)benzylamine), sulfinic acid salts (such as disodium hydroxysulfinoacetate), ferrous compounds (such as iron(II) sulfate, iron(III) chloride), tartaric acid or one of its salts, ascorbic acid or one of its salts, and mixtures thereof.

[0119] Preferably, the reducing agent is chosen from among the tertiary amines, more preferably from among the aromatic tertiary amines. For example, the reducing agent 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.

[0120] Advantageously, the reducing agent 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.

[0121] 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 -,

[0122] When the reducing agent 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.

[0123] Examples of azo initiators include 2,2'-azobisisobutyronitrile, 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-methylbutyronitrile), and mixtures thereof.

[0124] The photoinitiator is advantageously suited for use with irradiation sources emitting in the UV-visible range (particularly with wavelengths between 100 nm and 420 nm). For example, the UV-visible radiation source can be a broad-spectrum LED or lamp centered on UVA (wavelength range between 315 nm and 420 nm) of the iron-doped mercury type.

[0125] The photoinitiator can be chosen from the group consisting of type I, type II, and mixtures thereof. Type I and II photoinitiators are known to those skilled in the art. In particular, type I photoinitiators undergo unimolecular bond cleavage upon irradiation to produce free radicals, while type II photoinitiators undergo a bimolecular reaction where the excited state of the photoinitiator interacts with a second molecule (a coinitiator) to generate free radicals.

[0126] The type I photoinitiator can be chosen from:

[0127] - acetophenone, - alkoxyacetophenones (such as 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 4'-ethoxyacetophenone), preferably α-dialkoxyacetophenones, hydroxyalkylphenones (such as 3'-hydroxyacetophenone, 4'-hydroxyacetophenone, 2,2-dimethyl-2-hydroxyacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 2-hydroxy-2-methylpropiophenone), preferably α-hydroxyalkylphenones,

[0128] - aminoalkylphenones (such as 2-methyl-4'-(methylthio)-2-morpholino-propiophenone, 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone, 2-(4-(methylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone), preferably α-aminoalkylphenones,

[0129] - benzoin ethers (such as methyl benzoin ether, ethyl benzoin ether, isopropyl benzoin ether, isobutyl benzoin ether),

[0130] - phosphine oxides (such as diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), ethyl-(2,4,6-trimethylbenzoyl) phenylphosphinate (TPO-L, CAS: 84434-11-7), phenylbis-(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO, CAS: 162881-26-7), preferably acylphosphine oxides,

[0131] - metallocenes (such as ferrocene, bis[2,6-difluoro-3-(1 / 7-pyrrol-1-yl)phenyl]titanocene, iron(ll) (cumene)cyclopentadienyl hexafluorophosphate),

[0132] - benzile and its derivatives (such as 4,4'-dimethylbenzile),

[0133] - and their mixtures.

[0134] The type II photoinitiator can be chosen from:

[0135] - benzophenones (such as benzophenone, 4-phenylbenzophenone, 4-(4-methylphenylthio)benzophenone, 1-[4[(4-benzoylphenyl)thio]phenyl]-2-methyl-2-[(4-methylphenyl)sulfonyl]-1-propanone (CAS: 272460-97-6)), thioxanthones (such as isopropylthioxanthone (ITX), 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2-chlorothioxanthone, 1-chloro-4-isopropylthioxanthone),

[0136] - phenylglyoxylic acid esters (such as methyl phenylglyoxylate),

[0137] - dibenzylidene ketones (such as 1,5-bis[4-(dimethylamino)phenyl]-1,4-pentadien-3-one),

[0138] - coumarins (such as coumarin, 7-methoxycoumarin, 7-diethylaminocoumarin), - and their mixtures.

[0139] The priming agent content may be between 1% and 40% by weight relative to the total weight of component B, preferably between 5% and 30% by weight.

[0140] The priming agent content may be between 0.01% and 10% by weight relative to the total weight of the two-component composition, preferably between 0.1% and 5% by weight, more preferably between 0.5% and 3% by weight.

[0141] When a reducing agent is present, the weight ratio of reducing agent to peroxide can be between 0.2 and 5, preferably between 0.3 and 2.

[0142] Core-bark charge

[0143] Component A may further include a core-shell charge.

[0144] 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.

[0145] 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.

[0146] Unless otherwise stated, the standards mentioned throughout the application are those in effect on the date the application was filed.

[0147] 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).

[0148] Advantageously, the core polymer comprises (or is essentially made 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 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.

[0149] 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.

[0150] 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 di(meth)acrylate of ethylene glycol and di(meth)acrylate of 1,3-butanediol, 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.

[0151] 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.

[0152] Advantageously, the bark polymer comprises (or is substantially 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.

[0153] In particular, the bark polymer comprises (or is essentially composed 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. "Essentially composed" means 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, and more preferably less than 1% by weight.

[0154] 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.

[0155] Advantageously, the intermediate polymer comprises (or is substantially 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.

[0156] 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.

[0157] 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.

[0158] 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.

[0159] 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.

[0160] According to one embodiment, the core-bark charge comprises:

[0161] - a core comprising (or consisting essentially of) a core polymer comprising (or consisting essentially of) a butadiene homopolymer and / or a butadiene-styrene copolymer,

[0162] - 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

[0163] - 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.

[0164] The volume-mean diameter of the functionalized core-barrel filler can range from 10 to 900 nm, preferably from 20 to 700 nm, and more preferably from 20 to 500 nm. The volume-mean diameter can be measured by dynamic light scattering (DLS). Examples of commercially available core-barrel fillers include Clearstrength® (e.g., Clearstrength® XT100) and Durastrength® from Arkema, and Paraloid™ (Paraloid™ 2650A, Paraloid™ 2691A) from Dow.

[0165] 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.

[0166] Component A Additives

[0167] Component A may further comprise one or more additives, in particular selected from crosslinking agents, adhesion promoters, fillers (other than a core-shell filler), polymerization inhibitors, UV stabilizers (or antioxidants), plasticizers, rheological agents, acrylic polymers (other than a urethane (meth)acrylate polymer), pigments, solvents, and mixtures thereof.

[0168] Advantageously, component A comprises a mixture of additives selected from adhesion promoters, polymerization activators, polymerization inhibitors and rheological agents.

[0169] The total content of additives may be up to 30% by weight relative to the total weight of component A, preferably between 1% and 15% by weight.

[0170] The crosslinking agent can be a multifunctional (meth)acrylate. For example, the crosslinking agent may be selected 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.

[0171] The crosslinking agent content can be up to 5% by weight relative to the total weight of component A.

[0172] The adhesion promoter may be selected from silanes (such as aminosilanes, epoxilanes, and 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), metal di(meth)acrylates (such as zinc di(meth)acrylate, calcium di(meth)acrylate, and magnesium di(meth)acrylate), and mixtures thereof, preferably from methacrylate phosphate ester-based adhesion promoters, (meth)acrylic acid, metal di(meth)acrylates, and mixtures thereof, particularly a mixture of 2-hydroxyethyl phosphate ester(s). methacrylate, methacrylic acid and zinc dimethacrylate.

[0173] 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.

[0174] The filler can be chosen from organic fillers, mineral fillers, and mixtures thereof.

[0175] 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.

[0176] 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.

[0177] The mineral feed can be untreated or treated, for example with an organic acid including stearic acid.

[0178] 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.

[0179] In this text, the average particle size advantageously corresponds to the d50 particle size distribution, i.e., the maximum size of 50% of the smallest particles by volume, and can be measured with a particle size analyzer, particularly by laser diffraction on a MALVERN-type instrument (for example, according to ISO 13320). An example of an organic filler is any organic filler, particularly polymeric, commonly used in adhesive compositions.

[0180] 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.

[0181] The average particle size of the organic load may be less than or equal to 50 pm, preferably between 5 and 20 pm.

[0182] The filler content can be up to 10% by weight relative to the total weight of component A.

[0183] The polymerization inhibitor can be chosen from hydroquinone, methyl ether hydroquinone, 2,6-di-tert-butyl-4-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol (BHT), 2,4-dimethyl-6-tert-butylphenol (Topanol A), and mixtures thereof. Polymerization inhibitors prevent the monomers of component A from spontaneously polymerizing.

[0184] The polymerization inhibitor content can be up to 3% by weight relative to the total weight of component A, preferably between 0.01 and 1% by weight.

[0185] 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.

[0186] 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.The UV stabilizer (or antioxidant) content can be up to 3% by weight relative to the total weight of component A.

[0187] The plasticizer can be any plasticizer commonly used in the field of adhesives.

[0188] 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 MESA MO LL® 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.

[0189] The plasticizer content can be up to 8% by weight relative to the total weight of component A.

[0190] The rheological agent can be chosen from among thixotropic agents, for example from: fumed silica (hydrophilic and / or hydrophobic),

[0191] - 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.

[0192] By "waxes derived from castor oil" we mean waxes obtained from castor oil, in particular hydrogenated castor oil.

[0193] The term "amide waxes" refers to waxes comprising one or more compounds containing 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). Preferably, amide waxes are micronized, meaning they have an average particle size of less than 1 mm. Advantageously, amide waxes have an average particle size of less than 500 µm, preferably less than 100 µm, and more preferably less than 15 µm.

[0194] Preferably, the rheological agent is chosen from fumed silica, amide waxes, and mixtures thereof, in particular a mixture of hydrophobic fumed silica and amide wax.

[0195] 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.

[0196] The acrylic polymer (other than a urethane (meth)acrylate polymer) may be selected from acrylic block copolymers, polyester, epoxy and / or polyether (meth)acrylate polymers, and mixtures thereof.

[0197] 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-.

[0198] 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.

[0199] 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.

[0200] 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.

[0201] 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).

[0202] 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.

[0203] Examples of acrylic block copolymers include the Nanostrength® marketed by Arkema (such as M52, M75, M65).

[0204] The (meth)acrylate polymer (of the polyester, epoxy, and / or polyether type) may comprise between two and six (meth)acrylate groups, preferably exactly two (meth)acrylate groups. Preferably, the (meth)acrylate polymer is a methacrylate polymer.

[0205] The (meth)acrylate polymer (of the polyester, epoxy, and / or polyether type) 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. The number-average molecular weight can be determined by size-exclusion chromatography (SEC), for example, using polystyrene reference standards and tetrahydrofuran as the solvent.

[0206] The (meth)acrylate polymer (of the polyester, epoxy and / or polyether type) 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).

[0207] (Meth)acrylate polymers (of the polyester, epoxy and / or polyether type) are commercially available, notably from SARTOMER.

[0208] The polyester (meth)acrylate polymer can be obtained by reaction between a polycarboxylic acid and a polyol, forming a polyester polyol with several ester bonds, followed by esterification with (meth)acrylic acid. The epoxy (meth)acrylate polymer can be obtained by (meth)acrylation of a polyepoxide polymer, for example polyepoxide bisphenol A, polyepoxide polybutadiene and / or a polyepoxide polyunsaturated oil.

[0209] The polyether (meth)acrylate polymer can result from the esterification by (meth)acrylic acid of a polyether polyol, in particular polyethylene glycol and / or polypropylene glycol.

[0210] The acrylic polymer content (other than a urethane (meth)acrylate polymer) may be up to 20% by weight relative to the total weight of component A, preferably up to 10% by weight.

[0211] 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.

[0212] The pigment content can be up to 2% by weight relative to the total weight of component A.

[0213] The solvent can be any solvent suitable for acrylic adhesive compositions.

[0214] The solvent content can be up to 5% by weight relative to the total weight of component A.

[0215] Component B Additives

[0216] Component B may further include one or more additives, in particular selected from adhesion promoters, fillers (other than a core-bark filler), UV stabilizers (or antioxidants), plasticizers, rheological agents, pigments, solvents, and mixtures thereof.

[0217] Advantageously, component B comprises a mixture of additives selected from plasticizers and rheological agents.

[0218] The total additive content may be up to 99% by weight relative to the total weight of component B, preferably between 70% and 95% by weight. The total additive content 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.

[0219] The adhesion promoter may be chosen from aminosilanes, epoxilanes, phosphate ester-based adhesion promoters (other than those comprising an acrylic group), and mixtures thereof.

[0220] The adhesion promoter content can be up to 5% by weight relative to the total weight of component B.

[0221] The filler can be chosen from organic fillers, mineral fillers, and mixtures thereof.

[0222] 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.

[0223] 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.

[0224] The mineral feed can be untreated or treated, for example with an organic acid including stearic acid.

[0225] 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.

[0226] As an example of an organic filler, one can cite any organic filler, especially polymeric, commonly used in the field of adhesive compositions.

[0227] 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.

[0228] The average particle size of the organic filler may be less than or equal to 50 µm, preferably between 5 and 20 µm. The filler content may be up to 10% by weight relative to the total weight of component B.

[0229] 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.

[0230] The UV stabilizer (or antioxidant) content can be up to 1% by weight relative to the total weight of component B.

[0231] The plasticizer can be any plasticizer commonly used in the field of adhesives.

[0232] 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 MESA MO LL® 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.

[0233] 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.

[0234] The rheological agent can be chosen from among thixotropic agents, for example from: fumed silica (hydrophilic and / or hydrophobic),

[0235] - 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.

[0236] 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.

[0237] Preferably, the rheological agent is chosen from among the amide waxes.

[0238] 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.

[0239] 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.

[0240] The pigment content can be up to 5% by weight relative to the total weight of component B.

[0241] The solvent can be any solvent suitable for acrylic adhesive compositions.

[0242] The solvent content can be up to 8% by weight relative to the total weight of component B.

[0243] Others

[0244] Advantageously, the volume ratio of component A to component B is between 5 and 15, for example about 10.

[0245] By "approximately X", we aim for plus or minus 10% of the value of X. Advantageously, the two-component composition according to the invention does not comprise a urethane (meth)acrylate polymer obtained by a process using an isocyanate.

[0246] Advantageously, the two-component composition according to the invention has zero isocyanate monomer content.

[0247] One or more of the ingredients of the two-component composition according to the invention may be obtained from recycled and / or bio-based materials. For example, the monofunctional (meth)acrylate monomer (in particular methyl methacrylate) may be obtained from recycled materials and / or the urethane (meth)acrylate polymer may be obtained from bio-based materials. "Bio-based" means obtained from biological resources (in particular plants, microorganisms, animals, etc.), and may have undergone chemical modification.

[0248] According to one embodiment, the two-component composition according to the invention comprises:

[0249] - a component A comprising:

[0250] - between 20% and 80% by weight of a monofunctional (meth)acrylate monomer, preferably a monofunctional methacrylate monomer,

[0251] - between 5% and 45% by weight of a urethane (meth)acrylate polymer obtained without the use of isocyanate by a process comprising transurethanization polycondensation followed by a (meth)acrylate functionalization step, the transurethanization polycondensation preferably being carried out from a reaction medium comprising an aliphatic dicarbamate, an aliphatic diol polymer and a catalyst,

[0252] - optionally between 5% and 30% by weight of core-bark filler, and

[0253] - optionally up to 30% by weight of one or more additives, relative to the total weight of component A, and

[0254] - a component B comprising:

[0255] - between 1% and 40% by weight of an initiator, preferably a radical initiator, and

[0256] - up to 99% by weight of one or more additives, in particular chosen from adhesion promoters, fillers (other than a core-bark filler), UV 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 5 and 15.

[0257] 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.

[0258] The ingredients of this embodiment and their particular contents are as described above, including preferred embodiments and characteristics.

[0259] In particular, the two-component composition according to the invention comprises:

[0260] - a component A comprising:

[0261] - between 40% and 60% by weight of a monofunctional (meth)acrylate monomer, preferably a monofunctional C1-C4 methacrylate monomer,

[0262] - between 15% and 40% by weight of a urethane (meth)acrylate polymer obtained without the use of isocyanate by a process comprising transurethanization polycondensation followed by a (meth)acrylate functionalization step, the transurethanization polycondensation preferably being carried out from a reaction medium comprising an aliphatic dicarbamate, an aliphatic diol polymer and a catalyst, and the urethane (meth)acrylate polymer preferably being a urethane methacrylate polymer,

[0263] - optionally between 10% and 22% by weight of core-bark filler,

[0264] - optionally a reducing agent when a peroxide is used as an initiator, the reducing agent / peroxide weight ratio being between 0.2 and 5, and

[0265] - optionally between 1% and 15% by weight of one or more additives, relative to the total weight of component A, and

[0266] - a component B comprising:

[0267] - between 5% and 30% by weight of a primer, preferably chosen from peroxides and mixtures thereof, and - preferably between 70% and 95% by weight of one or more additives, in particular chosen from adhesion promoters, fillers (other than a core-bark filler), UV 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 5 and 15.

[0268] Preferably, the two-component composition according to the invention consists essentially of the ingredients mentioned above.

[0269] The ingredients of this embodiment and their particular contents are as described above, including preferred embodiments and characteristics.

[0270] Advantageously, the two-component composition according to the invention has a shear strength at 23°C on aluminum of at least 7 MPa. The shear strength can be measured according to ISO 4587, for example as shown in Example 1 below.

[0271] Method for preparing the two-component composition

[0272] 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.

[0273] 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.

[0274] In particular, the two-component composition according to the invention can be prepared by a process comprising: a step of synthesis of the urethane (meth)acrylate polymer without the use of isocyanate by a process comprising a transurethanization polycondensation followed by a (meth)acrylate functionalization step, then a step of mixing the urethane (meth)acrylate polymer with the other ingredients of component A.

[0275] The two-component composition according to the invention is as described above, including preferred embodiments and features. Thus, the process comprising transurethanation polycondensation followed by a (meth)acrylate functionalization step is as described above, including preferred embodiments and features, and the other ingredients of component A are as described above, including preferred embodiments and features. In particular, component A comprises a monofunctional (meth)acrylate monomer, optionally a core-shell filler, and optionally one or more additives.

[0276] When component B comprises several ingredients, the process for preparing the two-component composition according to the invention advantageously includes a step of mixing the ingredients of component B.

[0277] The mixing steps of the process for preparing the two-component composition according to the invention can be implemented at a temperature between 15°C and 40°C, preferably between 18°C ​​and 25°C.

[0278] Use of communication

[0279] 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 or wind power.

[0280] The two-component composition according to the invention is as described above, including preferred embodiments and features.

[0281] Substrate assembly process

[0282] The present invention also relates to a method for assembling substrates comprising:

[0283] - 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

[0284] - bringing the substrates into contact, then

[0285] - cross-linking of the composition.

[0286] The two-component composition according to the invention is as described above, including preferred embodiments and features. It is understood that, during the coating and contacting steps, the two-component composition according to the invention is in an uncrosslinked state.

[0287] 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).

[0288] The substrates can be identical or different.

[0289] A wide variety of substrates can be used. These can include, for example, plastic, glass, metal, and / or composite materials, particularly plastic and / or metal. Preferably, at least one substrate is metal, and more preferably, all substrates are metals.

[0290] The plastic can be PVC, polycarbonate, polymethyl methacrylate (PMMA), polystyrene and / or acrylonitrile butadiene styrene (ABS).

[0291] The metal can be pure or an alloy, for example aluminium and / or steel (including stainless steel and / or galvanised).

[0292] 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).

[0293] Article

[0294] 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.

[0295] The article can be obtained through the substrate assembly process according to the invention (including preferred embodiments and features).

[0296] The substrates are preferably as described above for the substrate assembly method according to the invention; in particular, the substrates are preferably metal. All the embodiments described above can be combined with one another. In particular, the various aforementioned constituents of the two-component composition, and especially the preferred embodiments, can be combined with one another.

[0297] The following examples are given purely to illustrate the invention and should not be interpreted as limiting its scope.

[0298] Examples

[0299] Ingredients and measurement methods implemented

[0300] The following ingredients were used:

[0301] MERACRYL® HEMA 98 (by Rohm): 2-Hydroxyethyl methacrylate, Compound 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,

[0302] Bisomer® PTE (by Geo Specialty Chemicals): mixture of ethoxylated para-toluidines (CAS: 103671-44-9), tertiary aromatic amine; Clearstrength® XT 100 (by Arkema): core-bark filler,

[0303] - Methacrylic acid (by Sigma-Aldrich),

[0304] SR9054 (by SARTOMER): methacrylate mixture comprising phosphate groups, adhesion promoter,

[0305] - AEROSIL® R 202 (by Evonik): hydrophobic pyrogenated silica (treated with dimethyl polysiloxane), rheological agent,

[0306] CRAYVALLAC® SLT (by Arkema): micronized amide wax, rheological agent,

[0307] DYMALINK® 708 (by Cray Valley, a Total company): zinc dimethacrylate (CAS: 13189-00-9), adhesion promoter,

[0308] MEHQ (by Sigma-Aldrich): methyl ether hydroquinone (CAS: 150-76-5), polymerization inhibitor,

[0309] UA1: urethane methacrylate oligomer according to the invention, comprising 3% by weight of methacrylic acid relative to the total weight of UA1, DMC (by Fisher Scientific): dimethyl carbonate (CAS: 616-38-6), Priamine™ 1074 (by CARGILL): dimeric diamine (fatty acid dimer), TBD (by Sigma-Aldrich): 1,5,7-triazabicyclo[4.4.0]dec-5-ene (CAS 5807-14-7), catalyst,

[0310] PTMO (by Sigma-Aldrich): poly(tetrahydrofuran) having a number-average molar mass of 650 g / mol, polyol, methacrylic anhydride (by Fisher Scientific): CAS: 760-93-0, PEROXAN BP -Paste 50 PF 1 (by PERGAN): 50% dibenzoyl peroxide paste, organic peroxide,

[0311] Vikoflex® 7170 (by Cargill): epoxy soybean oil (CAS: 8013-07-8), plasticizer.

[0312] UA1 preparation process

[0313] UA1 was synthesized in 3 steps from dimethyl carbonate, Priamine™ 1074, PTMO and methacrylic anhydride.

[0314] During the 1 ère In the first step, Priamine™ 1074 (1 molar equivalent), TBD (0.1 molar equivalent), and DMC (10 molar equivalents) were added to a flask equipped with a magnetic stirrer and stirred for 5 h at 80 °C. The reaction mixture was then cooled to room temperature. The liquid product was dried using a rotary evaporator (25 °C under reduced pressure for 6 h) to remove excess DMC and obtain a dicarbamate monomer. This excess DMC can be recovered for reuse.

[0315] The product obtained at the end of the 1 èreThe step was then introduced into a three-necked flask equipped with a mechanical stirrer, a Dean-Stark condenser, and connected to a vacuum pump. PTMO was added at a suitable molar ratio previously calculated using Carothers' theory to target a number-average molar mass of approximately 2000 g / mol. The temperature was gradually increased to 160 °C under a nitrogen flow and with stirring. Next, 10 mol% of KOCH3 catalyst was added (% relative to the dicarbamate monomer). After 1 h of reaction at 160 °C, the Dean-Stark condenser was removed, and the reaction mixture was placed under vacuum (400 mbar, 1 h). Finally, the pressure was carefully reduced to 0.5 mbar for 4 h. After cooling to room temperature under a nitrogen flow, the resulting oligomer was recovered without any purification.

[0316] Finally, the oligomer (1 molar equivalent) and 200 ppm of the stabilizer 4-methoxyphenol were introduced into a three-necked flask equipped with a mechanical stirrer. The flask was placed under a stream of nitrogen and heated to obtain the oligomer in a molten state. Methacrylic anhydride (4 molar equivalents) was carefully added dropwise. The temperature was then set to 105 °C and the reaction mixture was left for 6 hours. A high vacuum (0.5 mbar) was applied for an additional 2 hours. After cooling to room temperature under a stream of nitrogen, the product UA1 was recovered without any purification and contained 3 wt% of residual methacrylic acid from the synthesis (relative to the total wt% of the recovered product UA1).

[0317] Measurement methods

[0318] The maximum tensile stress, tensile stress at break, elongation at break, and Young's modulus were measured in accordance with ISO 37, at a constant speed of 100 mm / min, 23°C, and 50% relative humidity. Specifically, the following conditions were applied:

[0319] A standard dumbbell-shaped test specimen (H2), type 2, as illustrated in the international standard ISO 37, is used. The narrow part of the dumbbell used has a length of 20 mm, a width of 4 mm, and a thickness of 2 mm.

[0320] To prepare the dumbbell, the composition to be tested was poured into a Teflon mold, a PET (poly(ethylene terephthalate)) film was applied to cover the surface of the mold filled with the composition, and the composition was left to crosslink for 24 hours under standard conditions (23°C and 50% relative humidity).

[0321] The measurement principle consists of stretching a standard specimen in a tensile testing machine (for example, Zwick Roell 2.5KN), whose moving jaw travels at a constant speed of 100 mm / min, and recording:

[0322] - the maximum tensile stress (in MPa), which is the maximum tensile stress that the specimen can withstand without undergoing permanent deformation or breaking,

[0323] - the tensile strength at break (in MPa) which is the tensile stress at which the specimen breaks (also called TS for Tensile Strength in English),

[0324] - the elongation at break (in %) which is the elongation of the specimen corresponding to the stretch observed at the moment of breakage, and

[0325] - Young's modulus (in MPa) is the slope of the tangent at the origin of the curve carrying the tensile stress as a function of the elongation of the specimen.

[0326] The measurement is repeated for 5 test tubes, and the corresponding average of the results obtained is calculated.

[0327] Lap Shear Strength (LSS) was measured according to ISO 4587 at 23°C and 50% humidity. A 250 µm layer of the test composition was applied between two 2 mm thick 6060 aluminum plates (previously cleaned with isopropanol). The maximum strength and the breaking strength (the applied force leading to failure of the assembly) were measured 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. The measurement was repeated for 5 specimens, and the corresponding average of the results was calculated.

[0328] 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 (starting temperature 21°C). At the end of the test, the exothermic peak was determined to be the maximum observed temperature. Preparation of compositions according to the invention and comparative

[0329] Compositions 1 and 2 were prepared by introducing component 1A or 2A, respectively, and 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 and 2 and consists of:

[0330] - 29% of PEROXAN BP-Paste 50 PF 1,

[0331] - 66% of Vikoflex® 7170, and

[0332] - 5% of CRAYVALLAC ® SLT, the percentages being percentages by weight relative to the total weight of component B.

[0333] Components A and B were prepared separately by mixing their ingredients by centrifugation until homogenized (SpeedMixer™ mixer).

[0334] [Table 1]

[0335] Example 3: Properties of the compositions prepared in Example 2

[0336] 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.

[0337] [Table 2]

[0338] Composition 1 according to the invention exhibits slightly more structural properties than the comparative composition 2, as the tensile stresses and Young's modulus are higher for a lower elongation while maintaining a good level of shear strength.

[0339] Thus, composition 1 according to the invention can be used as a structural adhesive and has the further advantage of being able to be prepared without the use of isocyanate monomers for the synthesis of the urethane methacrylate oligomer, unlike the comparative composition 2. The operator's exposure to chemicals causing allergic or asthmatic symptoms or breathing difficulties through inhalation is therefore reduced.

[0340] Furthermore, the yellowing of composition 1 according to the invention over time is reduced compared to the comparative composition 2.

Claims

Demands 1. Two-component composition comprising: - a component A comprising: - a monofunctional (meth)acrylate monomer, and - a urethane (meth)acrylate polymer obtained without the use of isocyanate by a process comprising transurethanation polycondensation followed by a (meth)acrylate functionalization step, and - a component B comprising: - a primer.

2. Two-component composition according to claim 1, wherein the monofunctional (meth)acrylate monomer has the formula (I): CH2=C(R a )-COOR b , in which: - R a represents a hydrogen atom or a methyl group, preferably a methyl group, - R brepresents 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 hydrocarbon group possibly comprising one or more groups selected from ether, ester, hydroxyl, carbonyl, and mixtures thereof, more preferably an aliphatic hydrocarbon group comprising one or more hydroxyl groups.

3. Two-component composition according to claim 1 or 2, wherein the monofunctional (meth)acrylate monomer is selected from methyl methacrylate, tert-butyl methacrylate, 2-octyl methacrylate, isobornyl methacrylate, 3,3,5-trimethylcyclohexyl methacrylate, tert-butylcyclohexyl methacrylate, (octahydro-4,7-methano-1H-indenyl)methyl methacrylate, benzyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, and mixtures thereof, in particular hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, and their mixtures, for example hydroxyethyl methacrylate.

4. Two-component composition according to any one of claims 1 to 3, wherein polycondensation by transurethanization is carried out from a reaction medium comprising a polycarbamate and a polyol polymer, preferably a dicarbamate and a diol polymer.

5. Two-component composition according to claim 4, wherein the polycarbamate is obtained from a reaction medium comprising a primary diamine, preferably aliphatic, and an organocarbonate, preferably aliphatic, the organocarbonate not comprising a carbonate group involved in a ring.

6. Two-component composition according to claim 5, wherein the organocarbonate is selected from C1-C4 dialkyl carbonates, diphenyl carbonate, and mixtures thereof, preferably from C1-C4 dialkyl carbonates and mixtures thereof, more preferably from dimethyl carbonate, diethyl carbonate, and mixtures thereof.

7. Two-component composition according to any one of claims 4 to 6, wherein the polyol polymer is a polyether polyol, a polycarbonate polyol and / or a polyester polyol, preferably a polyether polyol.

8. Two-component composition according to any one of claims 1 to 7, wherein the initiator is a radical initiator selected from peroxides, azo initiators, photoinitiators, and mixtures thereof, preferably from peroxides and mixtures thereof, more preferably from organic peroxides and mixtures thereof.

9. Two-component composition according to claim 8, wherein the initiator is a peroxide and said composition further comprising a reducing agent introduced into component A.

10. Two-component composition according to any one of claims 1 to 9, wherein component A further comprises a core-shell filler.

11. Two-component composition according to any one of claims 1 to 10, wherein component A and / or B further comprises one or more additives.

12. A process for preparing the two-component composition according to any one of claims 1 to 11 comprising: a step of synthesizing the (meth)acrylate urethane polymer without the use of isocyanate by a process comprising transurethanization polycondensation followed by a (meth)acrylate functionalization step, and then a step of mixing the (meth)acrylate urethane polymer with the other ingredients of component A.

13. Use of the two-component composition according to any one of claims 1 to 11 as a coating or adhesive, preferably as an adhesive.

14. 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 any one of claims 1 to 11, then - bringing the substrates into contact, then - cross-linking of the composition.

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

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