(Meth)acrylate-based compound

Abstract

The present invention relates to a crosslinkable two-component composition and the use of such a composition, the composition comprising: · an organocopper derivative, · at least one (meth)acrylate compound M1 Component A containing the same, provided that when the organocopper derivative is not halogenated, Component A also contains a halogenated carboxylic acid; · the following formula (VI): [R a -SO2 - p ,Q p+ (VI) Component B containing at least one compound having which includes.​

Description

Technical Field

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

[0002] The present invention also relates to the use of such a composition in the repair of materials and / or in the semi-structural or structural adhesive bonding of materials, for example in the fields of transport, marine, assembly, electronic devices or construction.

Background Art

[0003] Acrylic compositions are known reaction systems that crosslink by radical polymerization. These are used as adhesives, mastics, and coatings. Radical polymerization is usually initiated by a redox system that brings about the generation of radicals by a redox reaction.

[0004] Most acrylic systems are two-component systems. The first component conventionally 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 of, for example, an organic peroxide, and polymerization begins.

[0005] Most current acrylic systems use a peroxide / amine pair to initiate the redox reaction. However, these systems suffer from many drawbacks, including stability problems, poor reactivity (especially with long open times), lack of versatility, etc.

[0006] There is a need for new compositions that can at least partially overcome one or more of these drawbacks.

[0007] In particular, there is a need for new compositions that have high reactivity (high cohesive build-up) regardless of the associated open time.

[0008] A. Composition The present invention relates to a crosslinkable two-component composition, which composition ●Organic copper derivative; ●At least one (meth)acrylate compound M1; Component A containing the same, provided that when the organic copper derivative of component A is not halogenated, component A also contains a halogenated carboxylic acid; ·The following formula (VI): [R a -SO2 - p ,Q p+ (VI) [In the formula, ·R a represents an aryl radical or a heteroaryl radical, and the heteroaryl and aryl are at least one of the following radicals: F, OH, C(O)OMe, NHC(O)Me, methyl (Me), CF3, OH, or SO2 - may be substituted by, ·Q represents Li, Na, K, or Zn, preferably Na or K; ·P represents 1 or 2] Component B containing at least one compound having is included.

[0009] In the context of the present invention, the term "alkyl" preferably means a linear or branched hydrocarbon-based radical containing 1 to 20 carbon atoms. For example, methyl, ethyl, and propyl can be mentioned.

[0010] In the context of the present invention, the term "C4-C20 alkyl" means a linear or branched alkyl containing 4 to 20 carbon atoms.

[0011] In the context of the present invention, the term "alkenyl" means a linear or branched hydrocarbon-based radical containing at least one double bond, and the radical preferably contains 2 to 20 carbon atoms. Examples include propenyl and butenyl.

[0012] ​In the context of the present invention, the term "alkynyl" means a linear or branched hydrocarbon-based radical containing at least one triple bond, preferably containing 2 to 20 carbon atoms.

[0013] In the context of the present invention, the term "aryl" means a monocyclic or bicyclic aromatic radical, preferably containing 6 to 12 carbon atoms. For example, phenyl can be mentioned.

[0014] In the context of the present invention, the term "arylalkyl" means an alkyl group substituted by an aryl group, preferably containing 7 to 20 carbon atoms. Examples of arylalkyl groups include, for example, benzyl.

[0015] In the context of the present invention, the term "alkylaryl" means an aryl group substituted by an alkyl group, preferably containing 7 to 20 carbon atoms.

[0016] In the context of the present invention, the term "heteroaryl" means a monocyclic or bicyclic aromatic radical containing at least one heteroatom (e.g., O, S, or N), preferably containing 4 to 12 carbon atoms. Examples include radicals such as furanyl, thiophenyl, pyrrolyl, pyridinyl, indolyl, or imidazolyl.

[0017] In the context of the present invention, the term "cycloalkyl" means a monocyclic or polycyclic, preferably monocyclic or bicyclic saturated system, preferably containing 3 to 12 carbon atoms, and the ring may be bridged or fused in pairs, for example, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, or a norbornyl group.

[0018] In the context of the present invention, the term "heterocycloalkyl" refers to a monocyclic or polycyclic, preferably monocyclic or bicyclic saturated system, preferably containing 3 to 12 carbon atoms and at least one heteroatom (e.g., O or N), and the ring may be bridged or fused in pairs.

[0019] In the context of the present invention, the term "cycloalkenyl" refers to a monocyclic or polycyclic system containing at least one double bond, preferably containing 3 to 12 carbon atoms, and the ring may be bridged or fused in pairs.

[0020] In the context of the present invention, the term "alkoxy" means an -O-alkyl radical.

[0021] Component A Organic copper derivative The composition according to the present invention contains an organic copper derivative, preferably an organic copper (II) derivative.

[0022] The organic copper derivative is halogenated or not halogenated. It is preferred that the organic copper derivative is not halogenated.

[0023] The organic copper complex can be selected from the group formed by the copper salt of formula (VII-1) or the copper complex of formula (VII-2): TIFF2025518746000001.tif73170 wherein, ·R and R’’ each independently represent an alkyl radical, a cycloalkyl radical, an aryl radical, or a heteroaryl radical, and the alkyl radical, cycloalkyl radical, aryl radical, and heteroaryl radical may be substituted by one or more halogen atoms, for example one or more fluorine atoms, ·R’ represents a hydrogen atom, an alkyl radical, a cycloalkyl radical, an aryl radical, or a heteroaryl radical, or R and R’ (or R’ and R’’) may be bonded to the same ring containing 5 to 8 carbon atoms, and the ring may contain at least one heteroatom (such as O or S). ·R''' represents an alkyl radical, a cycloalkyl radical, an aryl radical, or a heteroaryl radical, and the alkyl radical, cycloalkyl radical, aryl radical, and heteroaryl radical may be substituted by one or more halogen atoms, such as one or more fluorine atoms.

[0024] Among the copper salts of formula (VII-1), for example, copper(II) acetate (such as anhydrous or monohydrate), copper(II) monofluoroacetate, copper(II) difluoroacetate, copper(II) trifluoroacetate (such as anhydrous or monohydrate), copper(II) hexanoate, copper(II) ethyl-2-hexanoate, and mixtures thereof can be mentioned.

[0025] According to a preferred embodiment, in formula (VII-1), R''' represents an alkyl radical having 1 to 20 carbon atoms, preferably 1 to 7 carbon atoms, and the alkyl may be substituted by one or more halogen atoms, such as one or more fluorine atoms.

[0026] Among the copper complexes of formula (VII-2), for example, copper(II) hexafluoroacetylacetonate (Cu(hfacac)2), copper(II) trifluoroacetylacetonate (Cu(tfacac)2), copper(II) acetylacetonate (Cu(acac)2), and copper(II) bis(2-acetylcyclohexanone) can be mentioned, and their formulas are as follows: TIFF2025518746000002.tif71170

[0027] According to a preferred embodiment, in formula (VII-2), ·R represents an alkyl radical, a cycloalkyl radical, an aryl radical, or a heteroaryl radical, preferably an alkyl radical, ·R’ represents hydrogen, ·R’’ represents an alkyl radical, which may be substituted by one or more halogen atoms, for example one or more fluorine atoms.

[0028] The organocopper derivative is preferably a copper complex of formula (VII-2), and more specifically, copper(II) acetylacetonate (Cu(acac)2).

[0029] The total content of one or more organocopper derivatives, particularly organocopper derivatives of formula (VII-1) or formula (VII-2), may be in the range of 0.05 to 5% by weight, preferably 0.1 to 2% by weight, and even more preferably 0.2 to 1% by weight, based on the total weight of the crosslinkable two-component composition.

[0030] Halogenated carboxylic acid According to the present invention, when the organocopper derivative of component A defined above is not halogenated, component A also contains a halogenated carboxylic acid.

[0031] It should be noted that when the organocopper derivative is halogenated, component A may optionally contain a halogenated carboxylic acid.

[0032] The halogenated carboxylic acid may be selected from monohalogenated (containing one halogen atom), dihalogenated (containing two halogen atoms), or trihalogenated (containing three halogen atoms) carboxylic acids.

[0033] The halogenated carboxylic acid may be selected from the group consisting of monochloroacetic acid, monofluoroacetic acid, dichloroacetic acid, difluoroacetic acid, trichloroacetic acid, trifluoroacetic acid, and mixtures thereof.

[0034] The halogenated carboxylic acid is preferably selected from dichloroacetic acid, difluoroacetic acid, and mixtures thereof.

[0035] When one or more halogenated carboxylic acids are present, the total content of the carboxylic acid can be in the range of 0.5 to 20% by weight, preferably 0.5 to 10% by weight, and even more preferably 0.5 to 2% by weight, based on the total weight of the crosslinkable two-component composition.

[0036] (Meth)acrylate compound M1 Component A contains at least one (meth)acrylate compound M1.

[0037] (Meth)acrylate compound M1 can be a (meth)acrylate monomer, a (meth)acrylate oligomer, or a (meth)acrylate polymer.

[0038] (Meth)acrylate compound M1 is preferably a (meth)acrylate monomer.

[0039] (Meth)acrylate compound M1 can have the following formula (F): TIFF2025518746000003.tif29170In the formula, ·R 1 represents H or methyl, ·G represents an organic radical.

[0040] G is preferably selected from the group formed by alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkylaryl, arylalkyl, or aryl, and the alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkylaryl, arylalkyl, and aryl may be substituted, for example, by alkyl or hydroxy.

[0041] (Meth)acrylate compound M1 can have any of the following formulas (I), (II), (III), (VI), or (V): TIFF2025518746000004.tif162170 wherein, ·R 1 represents H or methyl, ·R 2 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 represents O, S, NH, or CH2, TIFF2025518746000005.tif9170 is a single bond or a double bond, provided that when Z represents O, TIFF2025518746000006.tif9170 it is a double bond, ·G’ is selected from the group consisting of alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkylaryl, or aryl, and the alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkylaryl, arylalkyl, and aryl may be substituted by an alkyl group, and the group G’ is characterized by not containing a heteroatom, ·G’’ is alkyl substituted by an OH group.

[0042] In the above formula (I), G’ is selected from the group consisting of C1-C20, preferably C4-C20 alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkylaryl, or aryl, and the alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkylaryl, arylalkyl, and aryl may be substituted by an alkyl group, and the group G’ is characterized by not containing a heteroatom.

[0043] In the above formula (I), G’ is preferably selected from the group consisting of alkyl (C1-C20, more preferably C4-C20), cycloalkyl, or aryl, and the alkyl, cycloalkyl, and aryl may be substituted by an alkyl group, and the group G’ is characterized by not containing a heteroatom. G’ is preferably also selected from cycloalkyl.

[0044] Among cycloalkyls, for example, isobornyl, tert-butylcyclohexyl, trimethylcyclohexyl, dicyclopentenyl, and tricyclodecyl can be mentioned.

[0045] Among the compounds of formula (I), for example, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-butyl (meth)acrylate, heptyl (meth)acrylate, 2-tert-butylheptyl (meth)acrylate, octyl (meth)acrylate, 3-isopropylheptyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, 5-methylundecyl (meth)acrylate, dodecyl (meth)acrylate, 2-methyldodecyl (meth)acrylate, tridecyl (meth)acrylate, tridecyl (meth)acrylate, 5-methyltridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, 2-methylhexadecyl (meth)acrylate, heptadecyl (meth)acrylate, 5-isopropylheptadecyl (meth)acrylate, 4-tert-butyloctadecyl (meth)acrylate, 5-ethyloctadecyl (meth)acrylate, 3-isopropyloctadecyl (meth)acrylate, octadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, bornyl (meth)acrylate, 2,3,4,5-tetra-t-butylcyclohexyl (meth)acrylate; benzyl (meth)acrylate, phenyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, isobornyl (meth)acrylate, and mixtures thereof can be mentioned.

[0046] The preferred compound M1 of formula (I) is as follows: TIFF2025518746000007.tif55170

[0047] Among the compounds M1 of the above formula (II), for example, the following monomers can be mentioned: TIFF2025518746000008.tif62170

[0048] Among the compounds M1 of the above formula (III), for example, the following monomers can be mentioned: TIFF2025518746000009.tif113170

[0049] Among the compounds M1 of formula (II) or (III), the following monomers and their mixtures are preferred: TIFF2025518746000010.tif94170

[0050] Among the compounds M1 of formula (V), for example, hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate can be mentioned.

[0051] The total content of one or more (meth)acrylate compounds M1 in component A can be 5% by weight or more, preferably 20% by weight or more, even more preferably 50% by weight or more, and even more advantageously 70% by weight or more based on the total weight of component A.

[0052] In the crosslinkable two-component composition according to the present invention, the content of one or more (meth)acrylate compounds M1 can be in the range of 5 to 99% by weight, preferably 20 to 99% by weight, even more preferably 50 to 99% by weight, and even more advantageously 75 to 99% by weight based on the total weight of the crosslinkable two-component composition.

[0053] (Meth)acrylate monomer M1 can be a recycled monomer or may not be a recycled monomer.

[0054] Photoinitiator P1 (optional) Component A may also contain photoinitiator P1.

[0055] The photoinitiator can be any photoinitiator known to those skilled in the art. Under the action of ultraviolet-visible light, radicals that usually initiate the photopolymerization reaction are generated by the photoinitiator, and in particular, it becomes possible to increase the effectiveness of the photopolymerization reaction. Needless to say, the photoinitiator is selected as a function of the light source used according to its ability to effectively absorb the selected radiation. For example, a suitable photoinitiator can be selected based on its ultraviolet-visible absorption spectrum. Advantageously, the photoinitiator is suitable for working with an irradiation source that emits in the vicinity of 300 to 420 nm. The source of ultraviolet (UV) or visible light can advantageously be an LED.

[0056] The photoinitiator P1 can be selected from the group consisting of the following: · Type I photoinitiators selected from the following: · Classes of acetophenone and alkoxyacetophenone, such as 2,2-dimethoxy-2-phenylacetophenone, and 2-diethyl-2-phenylacetophenone; · Classes of hydroxyacetophenone, 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; · Classes of alkylaminoacetophenone, such as 2-methyl-4'-(methylthio)-2-morpholinopropiophenone, 2-benzyl-2-(dimethylamino)-4-morpholinobutyrophenone, and 2-(4-(methylbenzyl)-2-(dimethylamino)-4-morpholinobutyrophenone; · Classes of benzoin ether, such as benzyl, benzoin methyl ether, and benzoin isopropyl ether: · Classes of 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); · Metallocene classes, such as ferrocene, titanium bis(eta 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluoro)-3-(1H-pyrrol-1-yl)phenyl, and iron(cumene)cyclopentadienyl hexafluorophosphate; · Type II photoinitiators selected from the following: · Classes of benzophenones, such as 4-phenylbenzophenone, 4-(4'-methylphenylthio)benzophenone, and 1-[4-[(4-benzoylphenyl)thio]phenyl]-2-methyl-2-[(4-methylphenyl)sulfonyl]-1-propanone; · Classes of thioxanthones, such as isopropylthioxanthone (ITX), 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2-chlorothioxanthone, and 1-chloro-4-isopropylthioxanthone; · Classes of benzoyl formates, such as methyl benzoyl formate; · Classes of dibenzylidene ketones, such as p-dimethylaminoketone; · Classes of coumarins, such as 5-methoxycoumarin and 7-methoxycoumarin, 7-diethylaminocoumarin, and N-phenylglycine coumarin; · Photoinitiators of classes of dyes, such as triazine, fluorone, cyanine, safranine, 4,5,6,7-tetrachloro-3',6'-dihydroxy-2',4',5',7'-tetraiodo-3H-spiro[isobenzofuran-1,9'-xanthene]-3-one, pyrylium and thiopyrylium, thiazine, flavin, pyronin, oxazine and rhodamine; · And mixtures thereof.

[0057] According to a preferred embodiment, the photoinitiator P1 is as follows: · Phosphine oxide type, 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); · Thioxanthone type, such as isopropylthioxanthone (ITX), 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2-chlorothioxanthone, and 1-chloro-4-isopropylthioxanthone; The photoinitiator P1 is selected from the above, and more preferably, the photoinitiator P1 is selected from diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO) and ethyl(2,4,6-trimethylbenzoyl)phenylphosphine oxide (TPO-L).

[0058] The total content of the photoinitiator P1 can be in the range of 0 to 5% by weight, preferably 0 to 2% by weight, and more preferably 0 to 1% by weight, based on the total weight of the crosslinkable two-component composition according to the present invention.

[0059] When present in the crosslinkable two-component composition according to the present invention, the content of the photoinitiator can be 0.01% by weight or more, for example, 0.1% by weight or more, based on the total weight of the composition.

[0060] Component B Compound of formula (VI) Component B contains at least one compound having the following formula (VI): [R a -SO2 - p ,Q p + (VI) In the formula, · R a represents an aryl radical or a heteroaryl radical, and the heteroaryl and aryl are at least one of the following radicals: ​F, OH, C(O)OMe, NHC(O)Me, methyl (Me), CF3, OH, or SO2 - may be substituted by · Q represents Li, Na, K, or Zn, preferably Na or K; · P represents 1 or 2.

[0061] The compound of formula (VI) may be selected from the following compounds: TIFF2025518746000011.tif181170

[0062] According to a preferred embodiment, the compound of formula (VI) is selected from the following compounds: TIFF2025518746000012.tif59170

[0063] The total content of one or more compounds of formula (VI) defined above may be in the range of 0.1 to 5.0% by weight, preferably 0.1 to 3.0% by weight, and even more preferably 0.2 to 1.5% by weight, based on the total weight of the crosslinkable two-component composition according to the present invention.

[0064] (Meth)acrylate compound Component B may contain one or more (meth)acrylate compounds M1 defined above for Component A.

[0065] Component B preferably contains the same one or more (meth)acrylate compounds M1 as Component A.

[0066] Component B may contain more than 5% by weight, preferably more than 20% by weight, advantageously more than 50% by weight, even more preferably more than 70% by weight, and even more preferably more than 90% by weight of one or more (meth)acrylate compounds M1, based on the total weight of Component B.

[0067] In particular, Component B contains 60 to 99.9% by weight, preferably 80 to 99.5% by weight, of one or more compounds M1, based on the total weight of Component B.

[0068] Component B's (meth)acrylate compound M1 preferably does not contain an acid group. The acid group can be a phosphate group, a thiophosphate group, a phosphonic acid group, a sulfonic acid group, and a carboxylic acid group. For example, the (meth)acrylate compound M1 in Component B is not dihydrogen 10-methacryloyloxydecyl phosphate.

[0069] Composition The crosslinkable two-component composition according to the present invention may contain at least one additive selected from the group consisting of a catalyst, a filler, an antioxidant, a polymerization inhibitor, a light stabilizer / UV absorber, a metal deactivator, an antistatic agent, an anti-fogging agent, a foaming agent, a biocide, a plasticizer, a lubricant, an emulsifier, a colorant, a pigment, a rheology agent, an impact modifier, an adhesion promoter, an accelerator, a fluorescent brightening agent, a flame retardant, a penetration inhibitor, a nucleating agent, a solvent, and mixtures thereof.

[0070] These additives may be present in Component A and / or Component B of the composition according to the present invention.

[0071] Examples of plasticizers that can be used include any plasticizer commonly used in the field of adhesives, which are, for example, epoxy resins, phthalates, benzoates, trimethylolpropane esters, trimethylolmethane esters, trimethylolethane esters, glycerol esters, pentaerythritol esters, naphthenic mineral oils, adipates, cyclohexyldicarboxylates, paraffin oils, natural oils (which may be epoxidized), polypropylenes, polybutylenes, hydrogenated polyisoprenes, and mixtures thereof.

[0072] For example, the following can be used: · Diisodecyl phthalate, for example, that commercially available under the name Palatinol (trademark) DIP by BASF. · Phenol ester of alkyl sulfonic acid, for example, that commercially available under the name Mesamoll (registered trademark) by Lanxess. · Diisononyl 1,2 - cyclohexanedicarboxylate, such as that commercially available under the name Hexamoll Dinch (registered trademark) by BASF, · Pentaerythritol tetravalerate, such as that commercially available under the name Pevalen (trademark) by Perstorp, · Epoxidized soybean oil, such as that commercially available under the name Vikoflex (registered trademark) 7170 by Arkema.

[0073] Examples of rheology agents (thixotropic agents) that can be used include any rheology agent commonly used in the field of adhesive compositions.

[0074] The thixotropic agent is preferably selected from the following: · PVC plastisol (corresponding to a suspension of PVC in a PVC - compatible plasticizer and obtained in situ by heating at a temperature in the range of 60 - 80 °C), such plastisol can be in particular those described in "Polyurethane Sealants", Robert M. Evans (ISBN 087762 - 998 - 6); · Fumed silica, such as that commercially available under the name HDK (registered trademark) N20 from Wacker, · Urea derivatives produced by the reaction of an aromatic diisocyanate monomer (e.g., 4,4'-MDI) and an aliphatic amine (e.g., butylamine), the production of such urea derivatives is described in particular in French Patent Application Publication No. 1591172 (FR 1 591 172): · Micro - sized amide wax, such as Crayvallac (registered trademark) SLT or Crayvallac (registered trademark) SLA commercially available from Arkema.

[0075] The composition according to the present invention may also contain at least one organic and / or inorganic filler.

[0076] The inorganic fillers that can be used are preferably selected such that the mechanical properties of the crosslinked composition according to the invention are improved.

[0077] Examples of inorganic fillers that can be used include any inorganic fillers that can be normally used in the field of adhesive compositions. These fillers are typically in the form of particles of various shapes. This can be, for example, spherical, fibrous, or irregular in shape.

[0078] The filler is preferably selected from the group consisting of clay, quartz, carbonate fillers, kaolin, gypsum, and mixtures thereof; preferentially, carbonate fillers, such as carbonates of alkali metals or alkaline earth metals, and more preferentially, calcium carbonate or chalk.

[0079] These fillers may or may not be treated, and may be treated, for example, with an organic acid such as stearic acid, or with a mixture of organic acids mainly formed from stearic acid.

[0080] Inorganic hollow microspheres (such as hollow glass microspheres), more specifically, those made of calcium sodium borosilicate or aluminosilicate, can also be used.

[0081] These fillers can be conductive and / or heat-conductive.

[0082] Among the conductive fillers, for example, carbon black, graphite, carbon fiber, metal M' (which may be coated with a layer of metal M''), inorganic or organic fillers coated with a layer of metal, and mixtures thereof can be mentioned.

[0083] Among the metals coated with a metal layer, for example, copper coated with a layer of silver can be mentioned.

[0084] The organic filler can be coated with a layer of metal (such as silver or copper). For example, polymethyl methacrylate (PPMA) coated with a layer of silver can be mentioned.

[0085] Among the heat-conductive fillers, for example, carbon black powder, graphite, carbon fiber (CNT), metal oxide, metal hydroxide, metal silicate, metal sulfide, boron nitride, and aluminum nitride can be mentioned. The metal of the metal compound is selected from, for example, tin, indium, antimony, aluminum, titanium, iron, magnesium, zinc, etc. The conductive and / or heat-conductive filler may be in the form of spherical particles, tubes, flakes or fibers, and in particular, the specific surface area is 0.01 m 2 / g to 100 m 2 / g and can be in the range.

[0086] This composition preferably contains a conductive filler.

[0087] The composition according to the present invention may contain one or more conductive and / or heat-conductive fillers in an amount of 0 to 95%, preferably 40 to 95% by weight, based on the total weight of the composition.

[0088] The conductive and / or heat-conductive filler is preferably in component B of the composition.

[0089] The composition according to the present invention may also contain at least one adhesion promoter (preferably selected from silanes such as aminosilane, epoxysilane, or acryloylsilane), or a phosphate ester-based adhesion promoter (such as a mixture of 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), 2-hydroxyethyl methacrylate monophosphate ester and diphosphate ester).

[0090] 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 a pigment is present, the pigment can, for example, account for 0.1 to 3% by weight, or 0.4 to 2%, based on the total weight of the composition.

[0091] The pigment can be an inorganic or organic pigment.

[0092] The pigment is, for example, TiO2, in particular Kronos® 2059 commercially available from Kronos.

[0093] The composition can contain at least one UV stabilizer or antioxidant in an amount of 0.1 to 3% by weight, preferably 1 to 3% by weight. These compounds are typically introduced to protect the composition from degradation resulting from reactions with oxygen that can be formed by the action of heat or light. These compounds can include primary antioxidants that scavenge free radicals. The primary antioxidants can be used alone or in combination with other secondary antioxidants or UV stabilizers.

[0094] Examples include Irganox® 1010, Irganox® B561, Irganox® 245, Irgafos® 168, Tinuvin® 328, or Tinuvin® 770 commercially available from BASF.

[0095] According to a preferred embodiment, the two-component composition according to the invention does not contain peroxides.

[0096] According to a preferred embodiment, the two-component composition according to the invention does not contain quaternary ammonium salts, such as dilauryl dimethyl ammonium chloride, or dodecyl trimethyl ammonium chloride.

[0097] In the composition according to the invention, the volume ratio of component A / component B can be in the range from 20 / 1 to 1 / 1, preferably in the range from 10 / 1 to 1 / 1. The volume ratio of A / B is preferably 1 / 1, but this volume ratio was not possible with peroxide / tertiary amine systems.

[0098] B. Ready-to-use kit The invention also relates to a ready-to-use kit packaged in two separate compartments, one containing component A as defined above and the other containing component B as defined above. This can be, for example, a two-component cartridge.

[0099] Specifically, the composition according to the invention can be in two-component form (e.g. in a ready-to-use kit, with component A in a first compartment or drum and component B in a second compartment or drum, in proportions suitable for direct mixing of the two components (e.g. using a metering pump)).

[0100] According to one aspect of the invention, the kit also has one or more means for mixing components A and B. The mixing means is preferably selected from a metering pump, a static mixer having a diameter appropriate for the amount used.

[0101] C. Use of the composition The invention also relates to the use of the crosslinkable two-component composition defined above as an adhesive, mastic or coating, preferably as an adhesive.

[0102] The invention also relates to the use of the composition in the structural or semi-structural repair and / or adhesive bonding of materials, for example in the fields of transport, automotive (passenger cars, buses or trucks), assembly, marine, electronic devices or construction.

[0103] The invention relates to a method of assembling two substrates by adhesive bonding, the method comprising: · mixing component A and B as defined above to form the composition as defined above; ·Coating at least one of the two substrates to be assembled with the composition, ·Effectively bringing the two substrates into contact, and then ·Crosslinking the composition is involved.

[0104] The crosslinking step can be carried out at a temperature between 0 °C and 200 °C, preferably between 10 °C and 150 °C, preferably between 23 °C and 80 °C, particularly between 20 °C and 25 °C.

[0105] Suitable substrates are, for example, inorganic substrates such as concrete, metals or alloys (e.g., aluminum alloys, steel, non-ferrous metals, and galvanized metals), or organic substrates such as wood, plastics (e.g., PVC, polycarbonate, PMMA, polyethylene, polypropylene, polyester, epoxy resin), metal substrates, and painted composite materials.

[0106] Crosslinking can be carried out under electromagnetic irradiation, for example, using a UV radiation source or an LED. The electromagnetic irradiation can be carried out on the bonding edge for an opaque substrate, or directly through the substrate for a transparent substrate.

[0107] The crosslinking step under electromagnetic irradiation can be carried out at a wavelength greater than 300 nm, preferably in the range of 360 nm to 680 nm, and even more preferably in the range of 360 nm to 420 nm.

[0108] The inventors have found that by specifically varying various parameters (e.g., the nature or content of one or more organic copper derivatives and / or one or more sulfinates), it is advantageously possible to vary the open time. The presence of the photoinitiator P1 and / or exposure to electromagnetic irradiation also advantageously makes it possible to shorten the open time.

[0109] Furthermore, the composition enables rapid build-up of cohesive force, advantageously regardless of the open time (short in the electronics field or long in the wind power field). Additionally, the composition according to the invention advantageously exhibits good adhesion properties and advantageously results in a tack-free surface after joining.

[0110] The composition according to the invention is advantageously suitable for transport as compared to peroxide-based compositions.

[0111] The invention also relates to a method for determining the crosslinking of the crosslinkable two-component composition defined above, the method comprising the step of mixing components A and B as defined above.

[0112] All embodiments defined above for the crosslinkable two-component composition and also for components A and B apply to this method.

[0113] The mixing step can be carried out in the range from 30 seconds to 1 minute.

[0114] During the initial mixing of components A and B, it is advantageous for the composition to be colored, in particular blue when the organic copper derivative is an organic copper(II) derivative. This allows checking that the mixing of parts A and B is uniform. During the crosslinking step, it is advantageous for the color of the composition to change.

[0115] This change in the color of the composition advantageously enables monitoring and determination of when the composition is polymerizing / crosslinking. This advantage avoids the additional use of colorants and allows simple visual confirmation of efficient mixing and effective polymerization / crosslinking, and thus easier use by the end user.

[0116] All of the above-described embodiments can be combined together. In particular, the various above components for the composition, in particular the preferred embodiments of the composition, can be combined together.

[0117] In the context of the present invention, the term "between x and y", or "ranging from x to y", means the region including the end values x and y. For example, the range "between 0% and 25%" specifically includes the values 0% and 25%.

[0118] The present invention will now be described with reference to the following examples, which are for illustrative purposes only and should not be construed as limiting the scope thereof.

[0119] Examples The following components were used: · SR (Registered Trademark) 506 D: Isobornyl acrylate (IBOA) (CAS No.: 5888-33-5) commercially available from Arkema, · SR (Registered Trademark) 531: Cyclic trimethylolpropane formal acrylate (CAS No.: 66492-51-1) commercially available from Arkema, · Cu(acac)2: Copper(II) acetylacetonate (CAS No.: 13395-16-9) from Sigma-Aldrich, · Cu(3FAA)2: Copper(II) trifluoroacetate anhydrous (CAS No.: 123333-88-0) from Sigma-Aldrich, · Sodium p-toluenesulfinate (CAS No.: 824-79-3), Sigma-Aldrich, · 2FAA: Difluoroacetic acid (CAS No.: 381-73-7), Sigma-Aldrich.

[0120] Example 1: Preparation of Composition 1 (According to the Present Invention) In a mixer under air with constant stirring, the components of Component A are mixed at a temperature of 23°C in the proportions shown in the following table.

[0121] In a mixer under air with constant stirring, the various components constituting Component B are mixed at a temperature of 23°C in the proportions shown in the following table.

[0122] [Table 1] TIFF2025518746000013.tif41170Component A and Component B are mixed at a volume ratio of 1:1 using a Sulzer (registered trademark) mixpac mixer at room temperature of 23°C.

[0123] Example 2: Preparation of Composition 2 (According to the Present Invention) In a mixer under air with constant stirring maintained, the components of Component A are mixed at a temperature of 23°C at the ratios shown in the following table.

[0124] In a mixer under air with constant stirring maintained, the various components constituting Component B are mixed at a temperature of 23°C at the ratios shown in the following table.

[0125] [Table 2] TIFF2025518746000014.tif52170Component A and Component B are mixed at a volume ratio of 1:1 using a Sulzer (registered trademark) mixpac mixer at room temperature of 23°C.

[0126] Example 3: Preparation of Composition 3 (According to the Present Invention) In a mixer under air with constant stirring maintained, the components of Component A are mixed at a temperature of 23°C at the ratios shown in the following table.

[0127] In a mixer under air with constant stirring maintained, the various components constituting Component B are mixed at a temperature of 23°C at the ratios shown in the following table.

[0128] [Table 3] TIFF2025518746000015.tif48170Component A and Component B are mixed at a volume ratio of 1:1 using a Sulzer (registered trademark) mixpac mixer at room temperature of 23°C.

[0129] Example 4: Performance of the Composition Measurement of Reactivity: Exothermicity is continuously analyzed using a pyrometer and also by thermal imaging.

[0130] The peak time is the time required to reach the peak temperature (the maximum exotherm seen during polymerization), which is different from the pot life (or lag time: the time required for the sample to initiate polymerization).

[0131] The time / temperature profile was created with an accuracy of ±1 °C for polymerizations of 2 g (height approximately 4.0 mm) and 0.25 g (height 1.4 mm) using an Omega OS552-V1-6 industrial infrared thermometer (Omega Engineering®, Inc., Stamford, Connecticut, USA).

[0132] Bonding test: Deposit Composition 1, 2, or 3 (obtained by mixing Components A and B obtained in Examples 1, 2, or 3, respectively, with a Sulzer® mixpac mixer) onto a first microscope slide glass (25 × 76 mm); · Attach a second microscope slide glass (25 × 76 mm) to the first slide glass that has received Composition 1, 2, or 3; · Slide the two microscope slide glasses to evenly distribute Composition 1, 2, or 3 between the two slide glasses (where oxygen exposure is reduced).

[0133] The bonding time is the time after which the two slide glasses cannot be separated.

[0134] Stability: · Close a bottle containing 10 g of Component A and a bottle containing 10 g of Component B (for any of Compositions 1, 2, or 3) in air and place them in an oven at 40 °C. ● Every week, collect 1.5 g of each component using a pipette and then place them in the two compartments of a medmix mixpac dual cartridge mixer (Sulzer). ● During mixing, the reactivity is monitored as before, using the apparatus described above to measure the peak time.

[0135] If this peak time is no longer observed, the preparation is declared unstable, whereas before that, the peak time would have been observed.

[0136] [Table 4] TIFF2025518746000016.tif53170nd=not determined

[0137] The peak times of Compositions 1, 2 and 3 according to the invention are advantageously short, highly exothermic and characterized by good reactivity (cohesive accumulation). The adhesion time is also short and there is no residual tack on the surface.

Claims

1. A crosslinkable two-component composition, ● Organic copper derivatives; ● At least one (meth)acrylate compound M1; Component A contains, provided that if the organocopper derivative of component A is not halogenated, component A also contains a halogenated carboxylic acid; • The following formula (VI): [R ａ -SO ２ － ] ｐ ,Q ｐ＋ (VI) [In the formula, ・R ａ represents an aryl group or a heteroaryl group, and the heteroaryl and aryl groups consist of at least one of the following groups: F, OH, C(O)OMe, NHC(O)Me, methyl (Me), CF ３ , OH, or SO ２ － may be substituted by, Q represents Li, Na, K, or Zn, preferably Na or K; [P represents either 1 or 2] Component B contains at least one compound having the following characteristics. A composition containing the following:

2. The organocopper derivative is a copper salt of formula (VII-1) or a copper complex of formula (VII-2): [In the formula, R and R'' each independently represent an alkyl group, cycloalkyl group, aryl group, or heteroaryl group, and the alkyl group, cycloalkyl group, aryl group, and heteroaryl group may be substituted with one or more halogen atoms, for example, one or more fluorine atoms. R' represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group, or R and R' (or R' and R'') may be bonded to the same ring containing 5 to 8 carbon atoms, and the ring may contain at least one heteroatom (e.g., O or S). R'' represents an alkyl group, cycloalkyl group, aryl group, or heteroaryl group, and the alkyl group, cycloalkyl group, aryl group, and heteroaryl group may be substituted with one or more halogen atoms, for example, one or more fluorine atoms. Selected from the group formed from, The composition according to claim 1, characterized in that...

3. The organocopper derivative is a copper salt of formula (VII-1), where R''' represents an alkyl group containing 1 to 20 carbon atoms, preferably 1 to 7 carbon atoms, and the alkyl group may be substituted with one or more halogen atoms, for example, one or more fluorine atoms. The composition according to claim 1, characterized in that...

4. The organocopper derivative is a copper salt of formula (VII-2), R represents an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group, preferably an alkyl group. R' represents hydrogen, R'' represents an alkyl group, and this alkyl group may be substituted with one or more halogen atoms, for example, one or more fluorine atoms. The composition according to claim 1, characterized in that...

5. The organic copper derivative of component A is not halogenated. The composition according to claim 1, characterized in that...

6. The total content of one or more organocopper derivatives is in the range of 0.05 to 5% by weight, preferably 0.1 to 2% by weight, and more preferably 0.2 to 1% by weight, relative to the total weight of the crosslinkable two-component composition. The composition according to claim 1, characterized in that...

7. The halogenated carboxylic acid is selected from monohalogenated (containing one halogen atom), dihalogenated (containing two halogen atoms), or trihalogenated (containing three halogen atoms) carboxylic acids. The composition according to claim 1, characterized in that...

8. The halogenated carboxylic acid is preferably selected from the group formed from monochloroacetic acid, monofluoroacetic acid, dichloroacetic acid, difluoroacetic acid, trichloroacetic acid, trifluoroacetic acid, and mixtures thereof. The composition according to claim 1, characterized in that...

9. If one or more halogenated carboxylic acids are present, the total content of such carboxylic acids is in the range of 0.5 to 20% by weight, preferably 0.5 to 10% by weight, and more preferably 0.5 to 2% by weight, relative to the total weight of the crosslinkable two-component composition. The composition according to claim 1, characterized in that...

10. The (meth)acrylate compound M1 is a (meth)acrylate monomer, a (meth)acrylate oligomer, or a (meth)acrylate polymer. The composition according to claim 1, characterized in that...

11. Compound M1 is given by the following formula (F): [In the formula, ・R １ This represents H or methyl, [G represents an organic group, and G is preferably selected from the group formed from alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkylaryl, arylalkyl, or aryl, and the alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkylaryl, arylalkyl, and aryl may be substituted with, for example, alkyl or hydroxyl.] Having, The composition according to claim 1, characterized in that...

12. Compound M1 is one of the following formulas (I), (II), (III), (IV), or (V): [In the formula, ・R １ This represents H or methyl, ・R ２ represents H, methyl, or ethyl. - p represents 0 or 1, • z represents H, O, S, alkyl group, benzyl group, aryl group, or alkoxy group. Y is O, S, NH, or CH ２ This represents, It is a single bond or a double bond, provided that Z represents O, It is a double bond, G' is selected from the group formed from alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkylaryl, arylalkyl, or aryl, and the alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkylaryl, arylalkyl, and aryl may be substituted with an alkyl group, and the group G' is characterized by not containing a heteroatom. G'' is an alkyl group substituted with an OH group. Having, The composition according to claim 1, characterized in that...

13. In formula (I), G' is selected from the group formed from C1 to C20, preferably C4 to C20, alkyl, cycloalkyl, or aryl groups, and the alkyl, cycloalkyl, and aryl groups may be substituted with alkyl groups, and the group G' does not contain a heteroatom. The composition according to claim 12, characterized in that...

14. The compound of formula (I) is methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-butyl (meth)acrylate, heptyl (meth)acrylate, 2-tert-butylheptyl (meth)acrylate, octyl (meth)acrylate, 3-isopropylheptyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, 5-methylundecyl (meth)acrylate, dodecyl (meth)acrylate, 2-methyldodecyl (meth)acrylate, tridecyl (meth)acrylate, 5-methyltridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, 2-methylhexadecyl Selected from (meth)acrylate, heptadecyl (meth)acrylate, 5-isopropylheptadecyl (meth)acrylate, 4-tert-butyloctadecyl (meth)acrylate, 5-ethyloctadecyl (meth)acrylate, 3-isopropyloctadecyl (meth)acrylate, octadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, bornyl (meth)acrylate, 2,3,4,5-tetra-t-butylcyclohexyl (meth)acrylate; benzyl (meth)acrylate, phenyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, isobornyl (meth)acrylate, and mixtures thereof. The compound of formula (II) contains the following monomers: Selected from, The compound of formula (III) contains the following monomers: Selected from, - The compound of formula (V) is selected from hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate. The composition according to claim 1, characterized in that...

15. The total content of one or more (meth)acrylate compounds M1 in component A is 5% by weight or more, preferably 20% by weight or more, more preferably 50% by weight or more, and even more favorably 70% by weight or more, relative to the total weight of component A. The composition according to claim 1, characterized in that...

16. The compound of formula (VI) is the following compound: A compound of formula (VI) is selected from the following, and is preferably one of the following compounds: A composition according to claim 1, selected from the following.

17. It contains at least one additive selected from the group formed from catalysts, fillers, antioxidants, polymerization inhibitors, light stabilizers / UV absorbers, metal deactivators, antistatic agents, antifogging agents, foaming agents, biocides, plasticizers, lubricants, emulsifiers, colorants, pigments, rheological agents, impact modifiers, adhesion promoters, accelerators, fluorescent whitening agents, flame retardants, penetration inhibitors, nucleating agents, solvents, and mixtures thereof. The composition according to claim 1, characterized in that...

18. The filler is a conductive or heat-conducting filler. The composition according to claim 17, characterized in that...

19. A ready-to-use kit packaged in two separate compartments, one containing component A as described in claim 1 and the other containing component B as described in claim 1.

20. Use of the crosslinkable two-component composition described in claim 1 as an adhesive, mastic, or coating, preferably as an adhesive.

21. A method for assembling two substrates by adhesive bonding, - Mixing components A and B as described in claim 1 to form the composition described in claim 1, - Coat at least one of the two substrates to be assembled with the composition. - To effectively bring the two substrates into contact, then, - Crosslinking the composition A method that involves

22. A method for determining the crosslinking of a crosslinkable two-component composition according to claim 1, comprising the step of mixing components A and B according to claim 1, wherein the composition is colored while components A and B are initially mixed, and the color of the composition changes during the crosslinking step. A method characterized by the following features.

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