(Meth)acrylate Monomer Composition

Abstract

(Meth)acrylate Monomer Composition The present invention relates to a two-component crosslinkable composition, Component A, a reducing agent, a metal salt selected from the group consisting of metal salts of (meth)acrylic acid, metal salts of itaconic acid, and mixtures thereof; at least one (meth)acrylate monomer M1, Component A, component B comprising an oxidizing agent; wherein the composition comprises at least one radical photoinitiator in component A and / or B, and the use thereof.

Description

[Technical field]

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

[0002] The invention also relates to the use of said compositions in the repair and / or semi-structural or structural bonding of materials in the transportation, marine, assembly, electronics or construction fields. [Background technology]

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

[0004] Most acrylic systems are two-component systems. The first component traditionally contains a reducing agent and a reactive monomer, and the second component contains an oxidizing agent. When the two components are mixed, the reducing agent induces cleavage of the O-O bond, for example an organic peroxide, initiating polymerization.

[0005] However, one of the challenges of this technique is the inhibition by oxygen, because oxygen present in the triplet state in air interacts with the radicals formed on the surface of the sample, preventing them from initiating polymerization. This inhibition is essentially manifested at the surface, since oxygen penetrates little or not at all deep depending on the basis weight deposited. Moreover, the polymerization reaction is often slow on surfaces exposed to atmospheric oxygen, and partially polymerized surfaces often remain sticky.

[0006] There is a need for new (meth)acrylic compositions that make it possible to at least partially overcome at least one of the abovementioned drawbacks. More particularly, there is a need for new (meth)acrylic compositions that make it possible to undergo rapid, deep polymerization and to obtain a non-sticky surface.

[0007] Furthermore, the constant aim of improving process productivity (throughput levels) in the electronics sector and elsewhere requires new compositions with improved cohesion, i.e. achieving minimum mechanical performance in a shorter time. [Brief description of the drawings]

[0008] [Figure 1] 1 shows a graph representing the breaking strength (MPa)=f(time (min)) of compositions No. 1 (curve 1) and No. 2 (curve 2, comparative). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] A. Composition The present invention relates to a two-component crosslinkable composition, said composition comprising: Component A, a reducing agent, a metal salt selected from the group consisting of metal salts of (meth)acrylic acid, metal salts of itaconic acid, and mixtures thereof; - of formula (I), (II) or (III) below: TIFF2024518838000001.tif77170In the formula, -R a represents H or methyl, -R b represents H, methyl or ethyl, -p represents 0 or 1, -Z represents H, O, S, an alkyl group, a benzyl group, an aryl group, or an alkoxy group; -Y is O, S, NH or CH 2- represents - TIFF2024518838000002.tif12170 is a single or double bond, When Z represents O, the bond TIFF2024518838000003.tif11170 is a double bond, at least one (meth)acrylate monomer M1 having one of the following formulas: Component A, component B comprising an oxidizing agent; Including, The composition is characterized in that it comprises in component A and / or B at least one radical photoinitiator.

[0010] In the context of the present invention, the term "alkyl" denotes a straight-chain or branched group preferably containing from 1 to 20 carbon atoms, for example methyl, ethyl and propyl.

[0011] In the context of this invention, the term "aryl" designates a mono- or bicyclic aromatic group preferably containing from 6 to 12 carbon atoms, for example phenyl.

[0012] In the context of this invention, the term "cycloalkyl" denotes a saturated, mono- or polycyclic, preferably mono- or bicyclic, system, preferably containing from 3 to 12 carbon atoms, such as a cyclopropyl, cyclopentyl, cyclohexyl or norbornyl group, the rings of which are optionally bridged or fused in pairs.

[0013] In the context of this invention the term "alkoxy" designates an --O-alkyl group.

[0014] Reducing Agent The reducing agent may be selected from tertiary amines, sodium metabisulfite, sodium bisulfite, transition metals, azo compounds, α-aminosulfones, and mixtures thereof.

[0015] Among the azo compounds, mention may be made, for example, of azoisobutyric acid.

[0016] Among the α-sulfones, mention may be made, for example, of bis(tolylsulfonylmethyl)benzylamine.

[0017] Among tertiary amines, for example, diisopropanol-p-toluidine (DIIPT), dimethyl-p-toluidine, dipropoxy-p-toluidine, dimethylaniline, N,N-dimethylaminomethylphenol, N,N-diisopropanol-p-chloroaniline, N,N-diisopropanol-p-bromoaniline, N,N-diisopropanol-p-bromo-m-methylaniline, N,N-dimethyl-p-chloroaniline, N,N-dimethyl-p-bromoaniline, N,N-diethyl-p-chloroaniline, N,N-diethyl-p-bromoaniline, N,N-diethyl-p-bromoaniline, N,N-dimethyl-p-bromoaniline, N,N-diethyl-p-chloroaniline, N,N-diethyl-p-bromoaniline, N,N-dimethyl-p-bromo ...dimethyl-p-bromoaniline, N,N-diethyl-p-bromoaniline, N,N-dimethyl-p TIFF2024518838000004.tif51170In the formula, m and n are, independently of one another, integers ranging from 1 to 150, preferably from 1 to 100, preferentially from 1 to 72, advantageously from 1 to 36 and even more advantageously from 1 to 18, - r is an integer ranging from 1 to 200, preferably from 1 to 104, preferentially from 1 to 72 and advantageously from 1 to 36, -R 1 represents a radical selected from the group consisting of linear or branched, saturated or unsaturated alkyl containing from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, (hetero)aryl containing from 6 to 12 carbon atoms and cycloalkyl containing from 3 to 12 carbon atoms, -v represents an integer in the range 0 to 5, -R 2 and R 3 represent, independently of one another, a halogen atom, a hydrogen atom or a linear or branched alkyl group containing from 1 to 12 carbon atoms, said alkyl group being optionally interrupted by at least one oxygen atom, -R 4 represents a hydrogen atom, an arylalkyl group or a linear or branched alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 12 carbon atoms and advantageously from 1 to 6 carbon atoms, - m + n > 2, preferably n + m ≧ 2.5; and mixtures thereof.

[0018] In the above formula (IV), the value of v is preferably 1, and R 1 is preferably in the para position.

[0019] The amine of formula (IV) is preferably -R 1 が , represents a saturated or unsaturated, linear or branched alkyl containing from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, preferentially R 1 represents methyl, m and n, independently of one another, represent integers ranging from 1 to 18, preferably from 1 to 9 and advantageously from 1 to 5, -R 2 and R 3 represent, independently of one another, a hydrogen atom or a linear or branched alkyl group containing from 1 to 12 carbon atoms, said alkyl group being optionally interrupted by at least one oxygen atom, preferably R 2 and R 3 represent hydrogen atoms, - m + n > 2, preferably n + m ≧ 2.5; is selected from.

[0020] Preferably, the amine of formula (IV) is -R 1 represents a linear or branched alkyl group containing 1 to 5 carbon atoms, and preferentially R 1 represents methyl, m and n, independently of one another, represent integers ranging from 1 to 18, preferably from 1 to 9 and advantageously from 1 to 5, -R 2 and R 3 represents a hydrogen atom, - m + n > 2, preferably n + m ≧ 2.5; It is something.

[0021] Among the amines of formula (IV), mention may be made, for example, of Bisomer® PTE (CAS number: 878391-30-1) sold by Geo Speciality Chemicals, Accelerator PT25E (CAS number: 878391-30-1) sold by Lanxess, N,N-bis(2-hydroxypropyl)-p-aniline (CAS number: 3077-13-2) available from Biosynth, N,N-bis(2-hydroxypropyl)-p-toluidine (CAS number: 38668-48-3) sold by BASF, Ethox ANA-10 (CAS number: 36356-83-9) available from Ethox Chemical.

[0022] In the above formula (V), the value of v is preferably 1, and R 1 is preferably in the para position.

[0023] The amine of formula (V) is preferably -R 1 represents a saturated or unsaturated, linear or branched alkyl containing from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, and preferentially R 1 represents methyl, - r represents an integer ranging from 1 to 36, preferably from 1 to 18 and advantageously from 1 to 10, -R 3 represents a halogen atom, a hydrogen atom or a linear or branched alkyl group containing from 1 to 12 carbon atoms, said alkyl group being optionally interrupted by at least one oxygen atom; -R 4 represents a hydrogen atom, an arylalkyl group, or a linear or branched alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 6 carbon atoms, is selected from.

[0024] Among the amines of formula (V), mention may be made, for example, of N-(2-hydroxyethyl)-N-methylaniline (CAS number: 93-90-3) available from Sigma-Aldrich and N-(2-hydroxyethyl)-N-methyl-p-toluidine (MHPT, CAS number: 2842-44-6) available from Parchem.

[0025] Preferably, component A comprises as reducing agent a tertiary amine, even more preferentially an amine of formula (IV) above.

[0026] Component A may contain a reducing agent in a total content in the range of 0.3 to 5% by weight, preferably 1 to 3% by weight, based on the total weight of Component A.

[0027] Metal salts The metal salt is selected from metal salts of (meth)acrylic acid, metal salts of itaconic acid, and mixtures thereof.

[0028] The metal salt of (meth)acrylic acid may be selected from zinc salt of (meth)acrylic acid, iron salt of (meth)acrylic acid, magnesium salt of (meth)acrylic acid, calcium salt of (meth)acrylic acid, and mixtures thereof.

[0029] The metal salt of (meth)acrylic acid may be selected from zinc diacrylate, zinc dimethacrylate, zinc monomethacrylate, iron diacrylate, iron dimethacrylate, iron monomethacrylate, calcium diacrylate, calcium dimethacrylate, calcium monomethacrylate, magnesium diacrylate, magnesium dimethacrylate, magnesium monomethacrylate, and mixtures thereof.

[0030] The metal salt of itaconic acid may be selected from zinc salt of itaconic acid, iron salt of itaconic acid, magnesium salt of itaconic acid, calcium salt of itaconic acid, and mixtures thereof.

[0031] Preferably, the metal salt is a metal salt of (meth)acrylic acid, more preferentially a zinc salt of (meth)acrylic acid, even more preferentially a zinc diacrylate or zinc dimethacrylate.

[0032] Such metal salts can be found commercially, for example, Dymalink® 708 (a zinc methacrylate salt) sold by Total, or the zinc itaconate salt (CAS number 64723-16-6) sold by Alfa Chemistry.

[0033] The total content of metal salts as defined above in component A may range from 0.1 to 5% by weight, preferably from 0.5 to 3% by weight and even more preferentially from 0.5 to 2% by weight, relative to the total weight of said component A.

[0034] (Meth)acrylate Monomer M1 Component A according to the present invention comprises at least one (meth)acrylate monomer M1 as defined above.

[0035] According to one embodiment, in the above formulas (I) and (II), Y represents an oxygen atom.

[0036] The (meth)acrylate monomer M1 can be chosen from the following monomers: TIFF2024518838000005.tif144170

[0037] The monomers M1 are preferably chosen from the monomers of formula (I) or (II). It is even more preferentially one of the following compounds or a mixture thereof: TIFF2024518838000006.tif39170

[0038] The total content of the (meth)acrylate monomers M1 in Component A may be 20% by weight or more, preferably 20 to 70% by weight, based on the total weight of Component A.

[0039] The total content of (meth)acrylate monomers M1 in the two-component crosslinkable composition according to the present invention may be in the range of 20 to 90% by weight, preferably 40 to 90% by weight, based on the total weight of said two-component crosslinkable composition.

[0040] Oxidizing agent The oxidizing agent may be selected from peroxides, organic salts of transition metals, compounds containing labile chlorine, and mixtures thereof.

[0041] The peroxide may be selected from organic peroxides, inorganic peroxides and mixtures thereof.

[0042] Among the inorganic peroxides, mention may be made of peroxodisulfate and its salts, such as ammonium peroxodisulfate, sodium peroxodisulfate and potassium peroxodisulfate.

[0043] Among the organic peroxides, mention may be made of cumene hydroperoxide, paramenthane hydroperoxide, tert-butyl peroxyisobutyrate, tert-butyl peroxybenzoate, tert-butyl peroxyneodecanoate, tert-amyl peroxypivalate, acetyl peroxide, benzoyl peroxide, dibenzoyl peroxide, 1,3-bis-(t-butylperoxyisopropyl)benzene, diacetyl peroxide, t-butylcumyl peroxide, tert-butyl peroxyacetate, cumyl peroxide 2,5-dimethyl-2,5-di-t-butylperoxyhexane, 2,5-dimethyl-2,5-di-t-butyl-peroxyhex-3-yne, 4-methyl-2,2-di-t-butylperoxypentane, and mixtures thereof.

[0044] Preferably, component B comprises benzoyl peroxide as the oxidizing agent.

[0045] Component B may contain an oxidizing agent whose total content is in the range of 9 to 50% by weight, preferably 10 to 40% by weight, based on the total weight of component B.

[0046] The composition according to the invention may typically comprise a redox system, a reducing agent contained in component A and an oxidizing agent contained in component B. For example, the following combinations may be mentioned: - Persulfates (oxidizing agents) / (sodium metabisulfite and / or sodium bisulfite) (reducing agents), -Organic peroxides (oxidizing agents) / tertiary amines (reducing agents), -Organic hydroperoxide (oxidizing agent) / transition metal (reducing agent).

[0047] Radical Photoinitiators The composition according to the invention can be polymerized or crosslinked under electromagnetic radiation.

[0048] The composition according to the invention may comprise from 0.1 to 5% by weight, preferably from 0.5 to 3% by weight and even more preferentially from 1 to 2% by weight of radical photoinitiator relative to the total weight of the composition.

[0049] Component A may contain a radical photoinitiator in a total content in the range of 0.1 to 3% by weight, preferably 0.5 to 2% by weight, based on the total weight of Component A.

[0050] The radical photoinitiator is preferably present in component A.

[0051] The radical photoinitiator can be any radical photoinitiator known to those skilled in the art. Under the action of UV / visible radiation, the radical photoinitiator generates radicals responsible for the initiation of the photopolymerization reaction, making it possible in particular to increase the efficiency of the photopolymerization reaction. This is of course selected as a function of the light source used, according to its ability to efficiently absorb the selected radiation. For example, it will be possible to select a suitable radical photoinitiator from its UV / visible absorption spectrum. Advantageously, the radical photoinitiator is suitable for working with a radiation source that emits in the near visible range. Advantageously, the UV or visible radiation source can be an LED or a UVA-centered broad spectrum lamp of the Delolux03S type.

[0052] The radical photoinitiator may be selected from the group consisting of: - a type I radical photoinitiator selected from -acetophenone and alkoxyacetophenones, for example 2,2-dimethoxy-2-phenylacetophenone and 2-diethyl-2-phenylacetophenone, -Hydroxyacetophenones, such as 2,2-dimethyl-2-hydroxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone and 2-hydroxy-4'-(2-hydroxypropoxy)-2-methylpropiophenone; -Alkylaminoacetophenones, such as 2-methyl-4'-(methylthio)-2-morpholinopropiophenone, 2-benzyl-2-(dimethylamino)-4-morpholinobutyrophenone and 2-(4-methylbenzyl)-2-(dimethylamino)-4-morpholinobutyrophenone, benzoin ethers, such as benzil, benzoin methyl ether and benzoin isopropyl ether, - phosphine oxides, such as diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), ethyl(2,4,6-trimethylbenzoyl)phenylphosphine oxide (TPO-L) and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylphenylphosphine oxide (BAPO); metallocenes, such as ferrocene, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium and (cumene)(cyclopentadienyl)iron hexafluorophosphate, - a type II radical photoinitiator selected from: - benzophenones, such as 4-phenylbenzophenone, 4-(4'-methylphenylthio)benzophenone or 1-[4-[(4-benzoylphenyl)thio]phenyl]-2-methyl-2-[(4-methylphenyl)sulfonyl]-1-propanone, -thioxanthones, such as isopropylthioxanthone (ITX), 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2-chlorothioxanthone and 1-chloro-4-isopropylthioxanthone; benzoylformic acid esters, for example methyl benzoylformate, -dibenzylidene ketones, for example p-dimethylamino ketone, - coumarins, such as 5-methoxy- and 7-methoxycoumarin, 7-diethylaminocoumarin and N-phenylglycinecoumarin; radical photoinitiators of the dye class, such as triazines, fluorones, cyanines, safranines, 4,5,6,7-tetrachloro-3',6'-dihydroxy-2',4',5',7'-tetraiodo-3H-spiro[isobenzofuran-1,9'-xanthen]-3-one, pyrylium and thiopyrylium, thiazines, flavins, pyronines, oxazines or rhodamines, and -A mixture of them.

[0053] Preferably, the radical photoinitiator is selected from the following radical photoinitiators: - phosphine oxides, such as diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), ethyl(2,4,6-trimethylbenzoyl)phenylphosphine oxide (TPO-L) and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylphenylphosphine oxide (BAPO); -thioxanthones, such as isopropylthioxanthone (ITX), 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2-chlorothioxanthone and 1-chloro-4-isopropylthioxanthone. The radical photoinitiator is even more preferentially selected from diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), ethyl(2,4,6-trimethylbenzoyl)phenylphosphine oxide (TPO-L) and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylphenylphosphine oxide (BAPO).

[0054] For example, when the UV or visible light radiation source is an LED, the radical photoinitiator can be, for example, 2,4,6-trimethylbenzoyldiphenylphosphine or TPO available from Lambson under the trade name Speedcure® TPO (CAS: 75980-60-8), for example, ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate or TPO-L available from Lambson under the trade name Speedcure® TPO-L (CAS: 84434-11-7), for example, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide or BAPO (CAS: 162881-26-7), for example, available from BASF under the trade name Irgacure® 819. 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone (CAS: 119313-12-1), available from BASF under the trade name Irgacure® 369; 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone (CAS: 71868-10-5), available from BASF under the trade name Irgacure® 907; 1-hydroxycyclohexyl phenyl ketone (CAS: 947-19-3), available from BASF under the trade name Irgacure® 184; 2-isopropylthioxanthone or ITX (CAS: 5495-84-1), available from BASF under the trade name Speedcure® 2-ITX; or mixtures thereof.

[0055] Polymerization Inhibitor The composition according to the invention may also include one or more polymerization inhibitors.

[0056] The total content of polymerization inhibitors is preferably less than or equal to 0.25% by weight, preferably less than or equal to 0.20% by weight and advantageously less than or equal to 0.10% by weight relative to the total weight of the composition.

[0057] The polymerization inhibitor can be any type of polymerization inhibitor known to those skilled in the art.

[0058] It may be selected, for example, from hydroquinone, hydroquinone monomethyl ether (4-hydroxyanisole, MEHQ), 1,4-benzoquinone, 1,4-naphthoquinone, catechol, pyrogallol, bisphenol A, para-(tert-butyl)phenol, phenothiazine, and mixtures thereof.

[0059] More preferably, the polymerization inhibitor is hydroquinone monomethyl ether (MEHQ).

[0060] Additives The two-component composition according to the present invention may comprise at least one additive selected from the group consisting of catalysts, fillers, antioxidants, light stabilizers / UV absorbers, metal deactivators, antistatic agents, antifilm agents, foaming agents, biocides, plasticizers, lubricants, emulsifiers, dyes, pigments, rheological agents, impact modifiers, adhesion promoters, optical brighteners, flame retardants, antiperspirants, nucleating agents, solvents and mixtures thereof.

[0061] These additives may be present in component A and / or component B of the composition according to the invention.

[0062] Examples of plasticizers that may be used include any plasticizer commonly used in the field of adhesives, such as epoxy resins, phthalates, benzoates, trimethylolpropane esters, trimethylolethane esters, trimethylolmethane esters, glycerol esters, pentaerythritol esters, naphthenic mineral oils, adipates, cyclohexyl dicarboxylates, paraffinic oils, natural oils (optionally epoxidized), polypropylene, polybutylene, hydrogenated polyisoprene, and mixtures thereof.

[0063] Preferably, diisodecyl phthalate, such as that sold under the name Palatinol® DIDP by BASF; esters of alkylsulfonic acids and phenols, for example those sold under the name Mesamoll® by Lanxess, diisononyl 1,2-cyclohexanedicarboxylate, sold for example under the name Hexamoll Dinch® by BASF, pentaerythritol tetravalerate, for example sold under the name Pevalen™ by Perstorp; epoxidized soybean oil, for example as sold under the name Vikoflex® 7170 by Arkema; is used.

[0064] Examples of (thixotropic) rheological agents that may be used include any rheological agent conventionally used in the field of adhesive compositions.

[0065] Preferably, the thixotropic agent is selected from the following: - PVC plastisols, which correspond to a suspension of PVC in a plasticizer miscible with PVC and are obtained in situ by heating to a temperature between 60° C. and 80° C. These plastisols may in particular be those described in the publication "Polyurethane Sealants", Robert M. Evans, ISBN 087762-998-6. fumed silica, for example as sold under the name HDK® N20 by Wacker; - urea derivatives resulting from the reaction of aromatic diisocyanate monomers, such as 4,4'-MDI, with aliphatic amines, such as butylamine. The preparation of such urea derivatives is notably described in patent application FR 1 591 172. - Micronized amide waxes such as Crayvallac® SLT or Crayvallac® SLA sold by Arkema.

[0066] The composition according to the invention may also comprise at least one organic and / or mineral filler.

[0067] The mineral fillers that may be used are advantageously selected so as to improve the mechanical performance of the composition according to the invention in the crosslinked state.

[0068] Examples of mineral fillers that can be used include any mineral fillers that are commonly used in the field of adhesive compositions. These fillers are typically provided in the form of particles of various shapes. They can be, for example, spherical or fibrous, or have an irregular shape.

[0069] Preferably, the filler is selected from the group consisting of clay, quartz, carbonate fillers, kaolin, gypsum, clay and mixtures thereof. Preferentially, the filler is selected from carbonate fillers, such as alkali metal or alkaline earth metal carbonates, more preferentially calcium carbonate or chalk.

[0070] These fillers may be untreated or may be treated with an organic acid, such as stearic acid or a mixture of organic acids consisting primarily of stearic acid.

[0071] Hollow mineral microspheres such as hollow glass microspheres, more specifically those made of calcium sodium borosilicate or aluminosilicate, may also be used.

[0072] According to one preferred embodiment, component B does not comprise mineral fillers, and even more preferentially the composition according to the invention does not comprise mineral fillers.

[0073] The composition according to the invention may also comprise at least one adhesion promoter, preferably chosen from silanes, such as aminosilanes, epoxysilanes or acryloylsilanes, or phosphate ester based adhesion promoters, for example 2-hydroxyethyl methacrylate phosphate ester, 2-methacryloyloxyethyl phosphate, bis(2-methacryloyloxyethyl phosphate), 2-acryloyloxyethyl phosphate, bis(2-acryloyloxyethyl phosphate), methyl-(2-methacryloyloxyethyl phosphate), ethyl-(2-methacryloyloxyethyl phosphate), mixtures of 2-hydroxyethyl methacrylate mono- and diphosphate esters.

[0074] When a solvent, particularly a volatile solvent, is present in the composition, its content is preferably 5% by weight or less, more preferably 3% by weight or less, based on the total weight of the composition.

[0075] Preferably, the content of the solvent in the composition is 0 to 5% by weight.

[0076] When a pigment is present in the composition, its content is preferably 3% by weight or less, more preferably 2% by weight or less, based on the total weight of the composition. When present, the pigment may account for, for example, 0.1 to 3% by weight or 0.4 to 2% by weight, based on the total weight of the composition.

[0077] The pigment may be an organic pigment or an inorganic pigment.

[0078] For example, the pigment is TiO 2 , in particular the Kronos® 2059 sold by Kronos.

[0079] The composition may contain at least one UV stabilizer or antioxidant in an amount of 0.1-3% by weight, preferably 1-3% by weight. These compounds are typically introduced to protect the composition from degradation due to reaction with oxygen, which is likely to be formed by the action of heat or light. These compounds may include primary antioxidants, which scavenge free radicals. Primary antioxidants may be used alone or in combination with other secondary antioxidants or UV stabilizers.

[0080] Mention may be made, for example, of Irganox® 1010, Irganox® B561, Irganox® 245, Irgafos® 168, Tinuvin® 328 or Tinuvin™ 770 sold by BASF.

[0081] The composition may include at least one acrylic block copolymer, which is typically an impact modifier.

[0082] The acrylic block copolymer is - 1 to 99% of at least one rigid block (A) whose glass transition temperature is at least 20°C higher than ambient temperature; - 1 to 99% by weight of at least one flexible block (B) whose glass transition temperature is at least 10°C lower than ambient temperature; It may be a copolymer comprising:

[0083] Preferably, the copolymer is a triblock comprising rigid block / flexible block / rigid block; At least one rigid block (A) of the copolymer advantageously has the formula CH 2 =C(CH 3 )-COOR i( In the formula, R i is linear or branched C 1 -C 3 Alkyl group, branched C 4 group, C 3 -C 8 Cycloalkyl groups, C 6 -C20 Aryl group, C 1 -C 4 C containing alkyl groups 7 -C 30 Arylalkyl group, heterocyclic group, or C 1 -C 4 at least one methacrylate-derived monomer unit of the formula (I) is a heterocyclylalkyl group containing an alkyl group; The flexible block (B) is advantageously (i) Formula CH 2 =CH-COOR j (In the formula, R j is linear or branched C 1 -C 12 and / or (ii) Formula CH 2 =C(CH 3 )-COOR k (In the formula, R k is a linear C 4 -C 12 Alkyl group or branched C 5 -C 12 monomer units derived from at least one methacrylate of Includes.

[0084] The rigid block (A) preferably comprises monomer units derived from methyl methacrylate monomers.

[0085] The rigid block (A) may also comprise at least one dialkylacrylamide monomer, such as N,N-dimethylacrylamide, whose linear or branched alkyl group contains from 1 to 10 carbon atoms.

[0086] The flexible block (B) preferably comprises monomer units derived from at least one monomer selected from butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, 2-ethylhexyl methacrylate, n-octyl acrylate, and mixtures thereof.

[0087] Preferentially, the copolymer is a polymethyl methacrylate / poly(n-butyl acrylate) / polymethyl methacrylate block copolymer.

[0088] Among the acrylic block copolymers, mention may be made, for example, of Nanostrength® sold by Arkema (M52, which contains 52% by weight of poly(n-butyl acrylate), or M75, which contains about 75% by weight of poly(n-butyl acrylate), or M65, which contains about 65% by weight of poly(n-butyl acrylate).

[0089] The composition may also include impact modifiers having a core-shell structure, typically known as "core-shell impact modifiers."

[0090] Impact modifiers are known to those skilled in the art and specifically include core-shell impact modifiers.

[0091] The core-shell impact modifier may be in the form of spherical particles. The weight average particle size (diameter) may range from 40 nm to 900 nm, preferably from 80 to 500 nm. The particle size may be measured using a Zetasizer (Malvern).

[0092] The core-shell impact modifiers can be obtained by any method known to those skilled in the art, for example by a multi-stage method such as that described in French patent 3 052 169 or European patent 2 465 884. In particular, the polymers are prepared by emulsion polymerization.

[0093] The core of the impact modifier may comprise a polymer L1 selected from isoprene homopolymer, butadiene homopolymer, isoprene-butadiene copolymer, isoprene-vinyl monomer copolymer, butadiene-vinyl monomer copolymer. The vinyl monomer may be selected from styrene, alkylstyrene, acrylonitrile, alkyl(meth)acrylate, butadiene or isoprene.

[0094] The shell is, for example, C 1 -C 12 The shell may comprise a polymer L2 obtained from a (meth)acrylic monomer such as selected from alkyl (meth)acrylates. 1 -C 4 Alkyl methacrylate monomer and / or C 1 -C 8 The polymer L2 is derived from an alkyl acrylate monomer.

[0095] Preferably, the shell comprises a polymer L2 derived from methyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and mixtures thereof.

[0096] According to one embodiment, the core-shell impact modifier comprises: a core comprising a polymer L1 which is a styrene-butadiene copolymer; a shell comprising a polymer L2, which is poly(methyl methacrylate) (PMMA); Includes.

[0097] The core-shell impact modifier may be commercially available. For example, Clearstrength® (e.g. Clearstrength® XT100) or Durastrength® products sold by Arkema may be mentioned. Paraloids (Paraloid2650A, Paraloid2691A) sold by Dow Corning may also be mentioned.

[0098] The total content of the impact modifier(s) in component A may range from 2 to 30% by weight, preferably from 5 to 20% by weight, relative to the total weight of component A.

[0099] The composition may comprise at least one urethane acrylate having a number average molecular weight greater than or equal to 2000 g / mol, preferentially greater than or equal to 4000 g / mol.

[0100] Urethane acrylates can be obtained by reaction of polyols with polyisocyanates and subsequent functionalization, for example with hydroxymethyl methacrylate.

[0101] Many commercially available urethane acrylates are available, notably from Sartomer.

[0102] In the composition according to the invention, the volume ratio of component A / component B may range from 20 / 1 to 1 / 1, preferentially from 10 / 1 to 1 / 1.

[0103] B. Ready-made kits The present invention also relates to a ready-made kit comprising both component A as defined above and component B as defined above packaged in two separate compartments. This may for example be a two-component cartridge.

[0104] Indeed, the composition according to the invention may be in the form of a two-component, e.g. ready-made kit, comprising both component A in a first compartment or drum and component B in a second compartment or drum in a proportion suitable for direct mixing of the two components, e.g. using a light duty pump.

[0105] According to one embodiment of the invention, the kit also comprises one or more means for mixing components A and B. Preferably, the mixing means are selected from metering pumps or static mixers with a diameter suitable for the amounts used.

[0106] C. Use of the Composition The present invention also relates to the use of a two-component crosslinkable composition as defined above as an adhesive, mastic or coating, preferably as an adhesive.

[0107] The invention also relates to the use of said compositions in the repair and / or structural or semi-structural bonding of materials in the transportation, vehicle (car, bus or truck), assembly, marine, electronics or construction sectors.

[0108] The present invention relates to a method for assembling two substrates by adhesive bonding, comprising the steps of: - coating at least one of the two substrates to be assembled with a composition obtained by mixing components A and B as defined above, and then - bringing two substrates into effective contact; - crosslinking the composition by subjecting it to electromagnetic radiation; The present invention relates to a method comprising the steps of:

[0109] The crosslinking step may be carried out at a temperature of 0°C to 200°C, preferably 10°C to 150°C, preferably 23°C to 80°C, in particular 20°C to 25°C.

[0110] Suitable substrates are inorganic substrates such as, for example, concrete, metals or alloys (aluminium alloys, steel, non-ferrous metals, galvanized metals, etc.) or other organic substrates such as, for example, wood, plastics such as PVC, polycarbonate, PMMA, polyethylene, polypropylene, polyester, epoxy resins, metallic substrates and composites coated with paint.

[0111] Crosslinking can be accomplished using a UV radiation source or an LED.

[0112] The crosslinking step under electromagnetic radiation may be carried out at wavelengths above 300 nm, preferably in the range from 360 nm to 680 nm, and even more preferentially from 360 nm to 420 nm.

[0113] Preferably, the electromagnetic irradiation step is at 300 mW / cm 2 Below, 200mW / cm is preferred 2 For example, 100mW / cm 2 It is performed at the following intensities:

[0114] The composition according to the invention advantageously provides at least one of the following benefits: -Good storage stability, -High reactivity, -Good adhesion performance after crosslinking, the dry, non-sticky surface of the crosslinked composition, which makes it possible to increase the productivity, in particular of industrial processes; - Very rapid increase in agglomeration (e.g. reaching lap shear mechanical performance levels of 5-6 MPa in less than 5 minutes), thereby advantageously improving process productivity and allowing for higher throughput.

[0115] All the above-mentioned embodiments may be combined with each other. In particular, the above-mentioned various components of the composition, in particular the preferred embodiments of the composition, may be combined with each other.

[0116] In the context of the present invention, the term "between x and y" or "in the range of x to y" means a range that includes the limits x and y. For example, the range "0% to 25%" expressly includes the values ​​0% to 25%.

[0117] The invention will now be described in the following examples, which are given purely by way of illustration and should not be construed as limiting its scope. EXAMPLES

[0118] The following raw materials were used: Speedcure® TPO-L (CAS: 84434-11-7), ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate, sold by Lambson; -Bisomere® PTE (CAS number: 103671-44-9), sold by GEO Specialty Chemicals; - Peroxan BP 50 PF1 sold by PERGAN is a paste containing 50% dibenzoyl peroxide; - Crayvallac® SLT sold by Arkema is a micronized amide wax used as a rheological agent; Visiomer® Glyfoma (CAS: 1620329-57-9), a mixture of glycerol formal methacrylate isomers sold by Evonik Industries and having a molar mass equal to 172.2 g / mol, SR9054 (CAS number: 1628778-81-3), a bifunctional acrylic adhesion promoter sold by Sartomer, - Aerosil® R202 (CAS number: 67762-90-7): sold by Evonik, 100±20m 2 Hydrophobic fumed silica (post-treated PDMS) with a specific surface area (BET) equal to 1000 nm / g. - Clearstrength® XT100, a core-shell impact modifier based on MBS (MMA-butadiene-styrene), sold by Arkema; - Vikoflex® 7170 sold by Arkema is an epoxidized soybean oil used as a plasticizer, - PRO22641, a difunctional urethane-methacrylate oligomer from Sartomer; - Dymalink® 708F, zinc bismethacrylate, available from Total; -Methacrylic acid sold by Arkema.

[0119] Example 1: Preparation of the composition In a dispersive mixer (Dispermat) with constant stirring under nitrogen, Crayvallac® SLT, 20% of the total amount of Visiomer Glyfoma, and Pro22641 are mixed at medium speed for 30 minutes at 25°C, then the mixture is brought to 65°C with vigorous stirring and then maintained at 65°C for 0.5 hours.

[0120] The mixture is then returned to 50° C. with moderate stirring and the remaining Visiomer® Glyfoma is added.

[0121] The Clearstrength® XT100 is introduced twice at 40° C. with moderate stirring to ensure good dispersion, and then the other ingredients constituting component A are added at 30° C. in the proportions shown in the table below, in the following order: methacrylic acid, SR9054, Bisomer® PTE, Dymalink® 708, Aerosil® R202, and finally TPO-L, protected from ambient light. Component A is shielded from ambient light.

[0122] Vikoflex® 7170 and Cray Vallac® SLT are introduced into a dispersive mixer (Dispermat) maintained under constant stirring and nitrogen and mixed at 25° C., then the mixture is brought to 65-70° C. and maintained at 65-70° C. with vigorous stirring for 30 minutes. The mixture is then cooled to 25° C. and Peroxan BP50 PF1 is introduced with stirring. TIFF2024518838000007.tif122170

[0123] The above components A and B were mixed in a volume ratio of 10:1 (component A:component B).

[0124] The mixture is carried out according to a given volume ratio using a static mixer at about 23° C. and deposited onto a substrate.

[0125] Comparative Composition No. 2 was prepared in a manner similar to that carried out for Composition No. 1. Comparative Composition No. 2 does not contain a radical photoinitiator or a metal salt of a methacrylate. TIFF2024518838000008.tif105170

[0126] The above components A and B were mixed in a volume ratio of 10:1 (component A:component B).

[0127] Example 2: Results Adhesion Test The adhesive bonds are made on an aluminium strip from Rocholl. A 250 μm thick Teflon wedge is used to define an area of ​​25×12.5 mm on the strip. This area is filled with the test composition and then a second strip of the same material is laminated. The adhesive bonds are then bonded to each of the two wafers under a UVA lamp (Delolux03S) at 20 mW / cm. 2 for 1 min (30 s per wafer) and then tested at various times in a lap shear test according to standard ISO 4587 (2003).

[0128] The purpose of the tensile test on a universal testing machine is to evaluate the maximum force (MPa) that can be applied to an assembly to separate it. With the aid of the tensile testing device it is possible to apply a shear stress up to failure to a lap joint placed between two rigid supports by applying tension to a support parallel to the surface of the assembly and to the main axis of the test specimen. The result recorded is the breaking force or stress. The shear stress is applied through the movable jaw of the tensile testing device, which is displaced at a rate of 5 mm / min. This tensile test method is carried out according to the definition in the standard ISO 4587.

[0129] FIG. 1 shows a graph representing the breaking strength (MPa)=f(time (min)) of compositions No. 1 (curve 1) and No. 2 (curve 2, comparative).

[0130] 1 shows that composition No. 1 according to the invention (curve 1) exhibits a faster increase in aggregation than comparative composition No. 2 (curve 2). Indeed, composition No. 1 can advantageously achieve a performance level of 5 MPa in less than 5 minutes, while comparative composition No. 2 requires more than 15 minutes to reach such a value.

[0131] Additionally, it was observed that the polymer obtained with Composition No. 1 advantageously dried (became tack-free) at the surface more quickly, so that oxygen did not have time to inhibit the surface.

[0132] Stability testing The stability of Composition 1 was also tested by a one month aging test at 40° C. The above adhesion test was performed comparing the formulation at t=0 with the formulation aged at t=1 month at 40° C.

[0133] The breaking strengths obtained after 24 hours are given in the table below. TIFF2024518838000009.tif22170

[0134] After aging Composition No. 1 for one month at 40° C., good retention of the adhesive bond is advantageously observed.

Claims

1. A two-component crosslinkable composition comprising: Component A, a reducing agent, a metal salt selected from the group consisting of metal salts of (meth)acrylic acid, metal salts of itaconic acid, and mixtures thereof; of formula (I), (II) or (III) below: During the ceremony, -R ａ represents H or methyl, -R ｂ represents H, methyl or ethyl, -p represents 0 or 1; -Z represents H, O, S, an alkyl group, a benzyl group, an aryl group or an alkoxy group; -Y is O, S, NH or CH ２－ represents － is a single or double bond, When Z represents O, a bond is a double bond, at least one (meth)acrylate monomer M1 having one of the following formulas: Component A comprising: - component B comprising an oxidizing agent; Including, The composition comprises in component A and / or B at least one radical photoinitiator.

2. 2. The composition of claim 1, wherein the reducing agent is selected from tertiary amines, sodium metabisulfite, sodium bisulfite, transition metals, azo compounds, α-aminosulfones, and mixtures thereof.

3. The reducing agent is a tertiary amine, even more preferentially a compound of formula (IV): During the ceremony, m and n are, independently of one another, integers ranging from 1 to 150, preferably from 1 to 100, preferentially from 1 to 72, advantageously from 1 to 36 and even more advantageously from 1 to 18, -R １ represents a radical selected from the group consisting of linear or branched, saturated or unsaturated alkyl containing from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, (hetero)aryl containing from 6 to 12 carbon atoms and cycloalkyl containing from 3 to 12 carbon atoms, -v represents an integer ranging from 0 to 5; -R ２ and R ３ represent, independently of one another, a halogen atom, a hydrogen atom or a linear or branched alkyl group containing from 1 to 12 carbon atoms, said alkyl group being optionally interrupted by at least one oxygen atom, -m+n>2, preferably n+m≧2.5; 2. The composition according to claim 1, characterized in that the amine is of the formula:

4. The radical photoinitiator is - Type I radical photoinitiators, acetophenone and alkoxyacetophenones, such as 2,2-dimethoxy-2-phenylacetophenone and 2-diethyl-2-phenylacetophenone, -hydroxyacetophenones, such as 2,2-dimethyl-2-hydroxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone and 2-hydroxy-4'-(2-hydroxypropoxy)-2-methylpropiophenone; -Alkylaminoacetophenones, such as 2-methyl-4'-(methylthio)-2-morpholinopropiophenone, 2-benzyl-2-(dimethylamino)-4-morpholinobutyrophenone and 2-(4-methylbenzyl)-2-(dimethylamino)-4-morpholinobutyrophenone, benzoin ethers, such as benzil, benzoin methyl ether and benzoin isopropyl ether, - phosphine oxides, such as diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), ethyl(2,4,6-trimethylbenzoyl)phenylphosphine oxide (TPO-L) and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylphenylphosphine oxide (BAPO), metallocenes, such as ferrocene, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium and (cumene)(cyclopentadienyl)iron hexafluorophosphate, and a type I radical photoinitiator selected from - type II radical photoinitiators, -benzophenones, such as 4-phenylbenzophenone, 4-(4'-methylphenylthio)benzophenone or 1-[4-[(4-benzoylphenyl)thio]phenyl]-2-methyl-2-[(4-methylphenyl)sulfonyl]-1-propanone, -thioxanthones, such as isopropylthioxanthone (ITX), 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2-chlorothioxanthone and 1-chloro-4-isopropylthioxanthone; benzoylformates, for example methyl benzoylformate, - dibenzylidene ketones, for example p-dimethylamino ketone, - coumarins, such as 5-methoxy- and 7-methoxycoumarin, 7-diethylaminocoumarin and N-phenylglycinecoumarin, and a type II radical photoinitiator selected from radical photoinitiators of the dye class, for example triazines, fluorones, cyanines, safranines, 4,5,6,7-tetrachloro-3',6'-dihydroxy-2',4',5',7'-tetraiodo-3H-spiro[isobenzofuran-1,9'-xanthen]-3-one, pyrylium and thiopyrylium, thiazines, flavins, pyronines, oxazines or rhodamines, - mixtures thereof, The composition according to claim 1, characterized in that it is selected from the group consisting of:

5. The radical photoinitiator is - phosphine oxides, such as diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), ethyl(2,4,6-trimethylbenzoyl)phenylphosphine oxide (TPO-L) and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylphenylphosphine oxide (BAPO), -thioxanthones, such as isopropylthioxanthone (ITX), 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2-chlorothioxanthone and 1-chloro-4-isopropylthioxanthone; 2. Composition according to claim 1, characterized in that the radical photoinitiator is selected even more preferentially from diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), ethyl(2,4,6-trimethylbenzoyl)phenylphosphine oxide (TPO-L) and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylphenylphosphine oxide (BAPO).

6. 2. Composition according to claim 1, characterized in that it comprises from 0.1 to 5% by weight, preferably from 0.5 to 3% by weight and even more preferentially from 1 to 2% by weight of radical photoinitiator relative to the total weight of the composition.

7. 2. The composition of claim 1, wherein the metal salt of (meth)acrylic acid is selected from zinc salt of (meth)acrylic acid, iron salt of (meth)acrylic acid, magnesium salt of (meth)acrylic acid, calcium salt of (meth)acrylic acid, and mixtures thereof.

8. 2. The composition of claim 1, wherein the metal salt of (meth)acrylic acid is selected from zinc diacrylate, zinc dimethacrylate, zinc monomethacrylate, iron diacrylate, iron dimethacrylate, iron monomethacrylate, calcium diacrylate, calcium dimethacrylate, calcium monomethacrylate, magnesium diacrylate, magnesium dimethacrylate, magnesium monomethacrylate, and mixtures thereof.

9. 2. The composition according to claim 1, characterized in that the metal salt of (meth)acrylic acid is a zinc salt, preferably zinc diacrylate or zinc dimethacrylate.

10. 2. The composition according to claim 1, characterized in that in formulas (I) and (II), Y represents an oxygen atom.

11. The (meth)acrylate monomer is selected from the group consisting of the following monomers:

2. The composition according to claim 1, characterized in that it is selected from:

12. 2. The composition according to claim 1, characterized in that component A comprises (meth)acrylate monomers M1 in a total content of at least 20% by weight, preferably from 20 to 70% by weight, relative to the total weight of component A.

13. 10. The composition of claim 1, comprising at least one additive selected from the group consisting of catalysts, fillers, antioxidants, light stabilizers / UV absorbers, metal deactivators, antistatic agents, anti-film forming agents, foaming agents, biocides, plasticizers, lubricants, emulsifiers, dyes, pigments, rheology agents, impact modifiers, adhesion promoters, optical brighteners, flame retardants, anti-fog agents, nucleating agents, solvents and mixtures thereof.

14. 2. Composition according to claim 1, characterized in that the volume ratio of component A / component B ranges from 20 / 1 to 1 / 1, preferentially from 10 / 1 to 4 / 1.

15. 2. Use of the composition according to claim 1 as an adhesive, mastic or coating, preferably as an adhesive.

16. 1. A method for assembling two substrates by adhesive bonding, comprising: - coating at least one of the two substrates to be assembled with the composition according to claim 1 obtained by mixing components A and B, and then - bringing two substrates into effective contact; - crosslinking the composition by subjecting it to electromagnetic radiation; A method comprising:

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