Composition based on (meth)acrylate compounds

Abstract

This invention relates to crosslinkable two-component compositions comprising: - Component A, which comprises: * an organocopper derivative; * at least one (meth)acrylate compound M1; * a compound having the following formula (X): P(O)(OR b (OR) c (OR) d ) - Component B, which comprises at least one compound having the following formula (VI): Formula (VI), wherein the crosslinkable bicomponent composition is characterized in that the total content of the compound of formula (X) is from 0.1% by weight to 20% by weight relative to the total weight of the composition.

Description

Technical Field

[0001] This invention relates to compositions based on (meth)acrylate compounds.

[0002] The present invention also relates to the use of the composition in, for example, in the fields of transportation, marine, assembly, electronics or construction, in the bonding and / or repair of semi-structural or structural adhesives of materials. Background Technology

[0003] Acrylic compositions are known reactive systems that are crosslinked via free radical polymerization. They are used as adhesives, mastics, and coatings. Free radical polymerization is typically initiated by redox systems that generate free radicals through redox reactions.

[0004] Most acrylic acid systems are two-component systems. The first component typically contains a reducing agent and a reactive monomer, while the second component contains an oxidizing agent. Once the two components are mixed, the reducing agent induces the breaking of O-O bonds, such as those in organic peroxides, and initiates polymerization.

[0005] Most current acrylic acid systems use peroxide / amine pairs to initiate redox reactions. However, these systems suffer from many drawbacks, such as stability issues, poor reactivity, particularly long open times, and lack of versatility.

[0006] A new composition is needed that allows at least partial overcoming of one or more of these drawbacks.

[0007] There is a particular need for novel compositions that are highly reactive (high cohesive building) and independent of the associated open time.

[0008] A. Composition This invention relates to crosslinkable two-component compositions, said compositions comprising: - Component A, which comprises: Organic copper derivatives; At least one (meth)acrylate compound; Compounds of formula (X): P(O)(OR) b (OR) c (OR) d ), where R b R c R d They may be the same or different, and are selected from hydrogen, alkyl, aryl, heteroaryl, alkenyl, and cycloalkyl, wherein the alkyl, aryl, heteroaryl, alkenyl, and cycloalkyl may optionally be substituted; - Component B, which comprises: - At least one compound having the following formula (VI): in: - R a This indicates an aryl or heteroaryl group, wherein the heteroaryl and aryl groups are optionally substituted with at least one of the following groups: F, OH, C(O)OMe, NHC(O)Me, methyl (Me), CF3, OH, or SO2. - ; - Q represents Li, Na, K or Zn, with Na or K being preferred; - p indicates 1 or 2; - Optional at least one (meth)acrylate compound; The crosslinkable two-component composition is characterized in that the total content of the compound of formula (X) is from 0.1% to 20% by weight relative to the total weight of the composition.

[0009] In the context of this invention, the term "alkyl" should be understood to refer to a straight-chain or branched hydrocarbon group, preferably a straight-chain or branched hydrocarbon group comprising 1 to 20 carbon atoms. Examples of such terms include methyl, ethyl, and propyl.

[0010] In the context of this invention, the terms "C4 to C" are used. 20 "Alkyl" should be understood as referring to straight-chain or branched alkyl groups containing 4 to 20 carbon atoms.

[0011] In the context of this invention, the term "alkenyl" refers to a straight-chain or branched hydrocarbon-based group comprising at least one double bond, preferably comprising 2 to 20 carbon atoms. Examples that may be mentioned include propenyl and butenyl.

[0012] In the context of this invention, the term "alkynyl" refers to a straight-chain or branched hydrocarbon-based group containing at least one triple bond, preferably containing 2 to 20 carbon atoms.

[0013] In the context of this invention, the term "aryl" refers to a monocyclic or bicyclic aromatic group, preferably a monocyclic or bicyclic aromatic group comprising 6 to 12 carbon atoms. For example, phenyl may be mentioned.

[0014] In the context of this invention, the term "arylalkyl" refers to an alkyl group substituted with an aryl group, which preferably contains 7 to 20 carbon atoms. For example, benzyl may be mentioned as an arylalkyl group.

[0015] In the context of this invention, the term "alkylaryl" refers to an aryl group substituted with an alkyl group, which preferably contains 7 to 20 carbon atoms.

[0016] In the context of this invention, the term "heteroaryl" refers to a monocyclic or bicyclic aromatic group containing at least one heteroatom, such as O, S, or N, and preferably a monocyclic or bicyclic aromatic group containing 4 to 12 carbon atoms. Examples that may be mentioned include furanyl, thiophene, pyrrole, pyridyl, indolyl, or imidazolyl.

[0017] In the context of this invention, the term "cycloalkyl" refers to a monocyclic or polycyclic saturated system, preferably a monocyclic or bicyclic saturated system, which preferably contains 3 to 12 carbon atoms, and the rings may be bridged or fused in pairs, such as cyclopropyl, cyclopentyl, cyclohexyl or norbornyl.

[0018] In the context of this invention, the term "heterocyclic alkyl" refers to a monocyclic or polycyclic saturated system, preferably a monocyclic or bicyclic saturated system, which preferably contains 3 to 12 carbon atoms and at least one heteroatom, such as O or N, wherein the rings may be fused or bridged in pairs.

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

[0020] In the context of this invention, the term "alkoxy" refers to –O-alkyl.

[0021] Component A Organocopper derivatives The compositions according to the invention comprise an organocopper derivative, preferably an organocopper(II) derivative.

[0022] The organocopper derivatives can be halogenated or non-halogenated. Preferably, the organocopper derivatives are non-halogenated.

[0023] The organocopper derivatives may be selected from copper salts of formula (VII-1) or copper complexes of formula (VII-2): in: - R and R'' independently represent alkyl, cycloalkyl, aryl or heteroaryl, wherein the alkyl, cycloalkyl, aryl and heteroaryl are optionally substituted by one or more halogen atoms, for example by one or more fluorine atoms; - R' represents a hydrogen atom, alkyl, cycloalkyl, aryl, or heteroaryl group. Alternatively, R and R' (or R' and R'') can be attached to the same ring containing 5 to 8 carbon atoms, which may optionally contain at least one heteroatom (e.g., O or S); - R''' represents alkyl, cycloalkyl, aryl, or heteroaryl, wherein the alkyl, cycloalkyl, aryl, or heteroaryl group is optionally substituted with one or more halogen atoms, for example, with one or more fluorine atoms.

[0024] Among the copper salts of formula (VII-1), references may be made to, for example, copper acetate (II) (e.g., anhydrous or monohydrate), copper monofluoroacetate (II), copper difluoroacetate (II), copper trifluoroacetate (II) (e.g., anhydrous or monohydrate), copper hexanoate (II), copper ethyl-2-hexanoate (II), and mixtures thereof.

[0025] According to a preferred embodiment, in formula (VII-1), R''' represents an alkyl group containing 1 to 20 carbon atoms, preferably 1 to 7 carbon atoms, wherein the alkyl group is optionally substituted with one or more halogen atoms, for example, with one or more fluorine atoms.

[0026] Among the copper complexes of formula (VII-2), examples such as copper(II) hexafluoroacetylacetonate (Cu(hfacac)2), copper(II) trifluoroacetylacetonate (Cu(tfacac)2), copper(II) acetylacetonate (Cu(acac)2), and bis(2-acetylcyclohexanone)copper(II) can be mentioned, each having the following formula: According to a preferred embodiment, in equation (VII-2): - R represents alkyl, cycloalkyl, aryl or heteroaryl, preferably alkyl; - R' represents hydrogen.

[0027] - R'' indicates an alkyl group that is optionally substituted with one or more halogen atoms, such as one or more fluorine atoms.

[0028] The organocopper derivatives are preferably copper complexes of formula (VII-2), and more particularly copper acetylacetonate (II) (Cu(acac)2).

[0029] The total content of the organocopper derivative, especially the organocopper derivative of formula (VII-1) or (VII-2), may be from 0.03% to 10% by weight, preferably from 0.1% to 2% by weight, and even more preferably from 0.1% to 1% by weight, relative to the total weight of the crosslinkable two-component composition.

[0030] Compound of formula (X) Preferably, in the compound of formula (X), R b R c and R d At least one of them represents hydrogen.

[0031] The preferred compounds of formula (X) are those that satisfy the following: - R b R c and R d At least one of them represents H; - R b R c and R d At least one of them represents an alkyl group, which may optionally be substituted.

[0032] Substituents can be selected from halogens, alkyl groups, aryl groups, amino groups, hydroxyl groups, and -OC(=O)-C(R). e =CH2 group, where R e It represents H or CH3.

[0033] The compounds of formula (X) are preferably selected from: phosphoric acid, phosphate esters of 2-hydroxyethyl methacrylate, such as 2-(methacryloyloxy)ethyl phosphate and bis[2-(methacryloyloxy)ethyl] phosphate, phosphate esters of 2-hydroxyethyl acrylate, such as 2-(acryloyloxy)ethyl phosphate and bis[2-(acryloyloxy)ethyl] phosphate, 2-ethylhexyl phosphate, such as 2-(ethylhexyl) phosphate and bis[2-(ethylhexyl)] phosphate, and mixtures thereof.

[0034] The compounds of formula (X) are preferably selected from: phosphoric acid, 2-(methacryloyloxy)ethyl phosphate, bis[2-(methacryloyloxy)ethyl] phosphate, 2-(acryloyloxy)ethyl phosphate, bis[2-(acryloyloxy)ethyl] phosphate, (2-ethylhexyl) phosphate, bis(2-ethylhexyl) phosphate, and mixtures thereof.

[0035] Even more preferably, the compound of formula (X) is selected from bis[2-(methacryloyloxy)ethyl] phosphate, bis(2-ethylhexyl) phosphate and mixtures thereof.

[0036] Compounds of formula (X) may be sold, for example, by Sigma-Aldrich.

[0037] Preferably, the total content of the compound of formula (X) is 0.5% to 10% by weight, and more preferably 1% to 2% by weight, relative to the total weight of the composition.

[0038] (meth)acrylate compounds Component A contains at least one (meth)acrylate compound.

[0039] (Meth)acrylate compounds can be (meth)acrylate monomers, (meth)acrylate oligomers, or (meth)acrylate polymers.

[0040] Preferably, the (meth)acrylate compound is a (meth)acrylate monomer.

[0041] (Meth)acrylate compounds can have the following formula (F): in: - R 1 Indicates H or methyl; - G indicates an organic group.

[0042] Preferably, G is selected from alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkylaryl, arylalkyl, or aryl, wherein the alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkylaryl, arylalkyl, and aryl groups are optionally substituted with, for example, alkyl or hydroxyl groups.

[0043] (Meth)acrylate compounds may have one of the following formulas (I), (II), (III), (IV) or (V): in: - R 1 Indicates H or methyl; - R 2 Indicates H, methyl, or ethyl; - p represents 0 or 1; and - Z represents H, O, S, alkyl, benzyl, aryl, or alkoxy; - Y represents O, S, NH or CH2; - Is it a single or double bond? The condition is that when Z represents O, then the key... It is a double bond; - G' is selected from alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkylaryl, arylalkyl or aryl, wherein the alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkylaryl, arylalkyl and aryl groups are optionally substituted with alkyl groups, and the group G' is characterized in that it does not contain heteroatoms; - G'' is an alkyl group substituted with an OH group.

[0044] In equation (I) above, G' can be selected from C1-C 20 Alkyl groups, preferably C4-C 20 Alkyl, or selected from cycloalkyl, alkenyl, cycloalkenyl, alkylaryl, arylalkyl or aryl, wherein the alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkylaryl, arylalkyl and aryl are optionally substituted with alkyl, and the group G' is characterized in that it does not contain any heteroatoms.

[0045] In the above formula (I), G' is preferably selected from alkyl groups (preferably C1 to C2). 20 Alkyl, and even more preferably C4 to C5 20 The group G' is characterized by not containing any heteroatoms. More preferably, G' is selected from cycloalkyl and arylalkyl groups.

[0046] Among cycloalkyl groups, examples such as isobornyl, tert-butylcyclohexyl, trimethylcyclohexyl, dicyclopentenyl, and tricyclodecyl may be mentioned.

[0047] Among the compounds of formula (I), for example, methyl methacrylate, 2-ethylhexyl methacrylate, n-butyl methacrylate, heptyl methacrylate, 2-tert-butylheptyl methacrylate, octyl methacrylate, 3-isopropylheptyl methacrylate, nonyl methacrylate, decyl methacrylate, undecyl methacrylate, 5-methylundecyl methacrylate, dodecyl methacrylate, 2-methyldodecyl methacrylate, tridecyl methacrylate, 5-methyltridecyl methacrylate, tetradecyl methacrylate, pentadecyl methacrylate, and hexadecyl methacrylate may be mentioned. 2-Methylhexadecyl (meth)acrylate, heptadecanyl (meth)acrylate, 5-isopropylheptadecanyl (meth)acrylate, 4-tert-butyloctadecyl (meth)acrylate, 5-ethyloctadecyl (meth)acrylate, 3-isopropyloctadecyl (meth)acrylate, octadecyl (meth)acrylate, nonadecanyl (meth)acrylate, eicosyl (meth)acrylate, borneol (meth)acrylate, 2,3,4,5-tetra-tert-butylcyclohexyl (meth)acrylate; benzyl (meth)acrylate, phenyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, isoborneol (meth)acrylate, and mixtures thereof.

[0048] The preferred compounds of formula (I) are as follows: And benzyl methacrylate.

[0049] In the compounds of formula (II) above, the following monomers may be mentioned, for example: In the compounds of formula (III) above, the following monomers may be mentioned, for example: In compounds of formula (II) or (III), the following monomers and mixtures thereof are preferred: Among the compounds of formula (V), examples such as hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate may be mentioned.

[0050] Preferably, the (meth)acrylate compound is selected from: - Compounds of formula (III); - Compounds of formula (V).

[0051] More preferably, the (meth)acrylate compound is selected from: β-(meth)acrylate benzyl ester, - Hydroxyethyl (meth)acrylate, - The following compounds (III-F), - The following compounds (II-A), - The following compounds (III-A); - and its mixtures.

[0052] The total content of (meth)acrylate compounds in component A may be greater than or equal to 20% by weight, preferably greater than or equal to 50% by weight, and even more preferably greater than or equal to 70% by weight, relative to the total weight of component A.

[0053] The content of the (meth)acrylate compound in the crosslinkable two-component composition according to the invention may be from 5% to 99.95% by weight, preferably from 20% to 99% by weight, even more preferably from 50% to 99% by weight, and even more advantageously from 75% to 99% by weight, relative to the total weight of the crosslinkable two-component composition according to the invention.

[0054] (Meth)acrylate monomers may optionally be recycled monomers.

[0055] (Meth)acrylate compounds can be partially or fully bio-based.

[0056] Halogenated carboxylic acids (optional) The composition may further comprise a halocarboxylic acid.

[0057] Halogenated carboxylic acids can be selected from monohalogenated (containing one halogen atom), dihalogenated (containing two halogen atoms), or trihalogenated (containing three halogen atoms) carboxylic acids.

[0058] Halogenated carboxylic acids can be selected from monochloroacetic acid, monofluoroacetic acid, dichloroacetic acid, difluoroacetic acid, trichloroacetic acid, trifluoroacetic acid, and mixtures thereof.

[0059] Preferably, the halocarboxylic acid is selected from dichloroacetic acid, difluoroacetic acid, and mixtures thereof.

[0060] When present, the total content of halocarboxylic acids may be from 0.5% to 20% by weight, preferably from 0.5% to 10% by weight, and even more preferably from 0.5% to 2% by weight, relative to the total weight of the crosslinkable two-component composition.

[0061] Photoinitiator P1 (optional) Component A may also contain photoinitiator P1.

[0062] The photoinitiator can be any photoinitiator known to those skilled in the art. Under ultraviolet-visible radiation, the photoinitiator typically generates free radicals that will be responsible for initiating the photopolymerization reaction, and in particular, can increase the effectiveness of the photopolymerization reaction. Of course, the photoinitiator is selected based on the light source used and 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 use with radiation sources emitting in the near-field region of 300 to 420 nm. Advantageously, the ultraviolet or visible radiation source can be an LED.

[0063] Photoinitiator P1 can be selected from: - Type I photoinitiators, selected from: - Acetophenone and alkoxyacetophenone family, such as 2,2-dimethoxy-2-phenylacetophenone and 2-diethyl-2-phenylacetophenone; - The hydroxyacetophenone family, such as 2,2-dimethyl-2-hydroxyacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone and 2-hydroxy-4'-(2-hydroxypropoxy)-2-methylphenylacetone; - The alkylaminoacetophenone family, such as 2-methyl-4'-(methylthio)-2-morpholinylacetophenone, 2-benzyl-2-(dimethylamino)-4-morpholinylacetophenone and 2-(4-(methylbenzyl)-2-(dimethylamino)-4-morpholinylacetophenone; - The benzoin family, such as benzyl, benzoin methyl ether and benzoin isopropyl ether; - Phosphine oxide family, 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 family, such as ferrocene, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro)-3-(1H-pyrrolo-1-yl)phenyl)titanium and (cumene)(cyclopentadienyl)ferric hexafluorophosphate; - Type II photoinitiators, selected from: - The benzophenone family, such as 4-phenylbenzophenone, 4-(4'-methylphenylthio)benzophenone and 1-[4-[(4-benzoylphenyl)thio]phenyl]-2-methyl-2-[(4-methylphenyl)sulfonyl]-1-propanone; - Thioxanone family, such as isopropylthioxanone (ITX), 2,4-diethylthioxanone, 2,4-dimethylthioxanone, 2-chlorothioxanone and 1-chloro-4-isopropylthioxanone; - Benzoyl carbamate family, such as methyl benzoate; - Dibenzylidene ketone family, such as p-dimethylaminoketone; - The coumarin family, such as 5-methoxycoumarin and 7-methoxycoumarin, 7-diethylaminocoumarin and N-phenylglycinecoumarin; - Photoinitiators of the dye family, such as triazine, fluorescein, anthocyanin, saffron, 4,5,6,7-tetrachloro-3',6'-dihydroxy-2',4',5',7'-tetraiodo-3H-spiro[isobenzofuran-1,9'-xanthan]-3-one, pyranonium and thiopyranonium, thiazides, flavins, pyridines, oxazines and rhodamine; - and its mixtures.

[0064] According to a preferred embodiment, the photoinitiator P1 is selected from: - Phosphine oxide family, 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); - Thioxanone family, such as isopropylthioxanone (ITX), 2,4-diethylthioxanone, 2,4-dimethylthioxanone, 2-chlorothioxanone and 1-chloro-4-isopropylthioxanone; The photoinitiator P1 is even more preferably selected from diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO) and ethyl(2,4,6-trimethylbenzoyl)phenylphosphine oxide (TPO-L).

[0065] The total content of photoinitiator P1 may be 0% to 5% by weight, preferably 0% to 2% by weight, and even more preferably 0% to 1% by weight, relative to the total weight of the crosslinkable two-component composition according to the invention.

[0066] If photoinitiator P1 is present in the two-component composition according to the invention, the content of photoinitiator P1 may be greater than or equal to 0.01% by weight, for example, greater than or equal to 0.1% by weight, relative to the total weight of the composition.

[0067] Component B Compounds of formula (VI) Component B comprises at least one compound having the following formula (VI): [R a -SO2 - ] p Q p+ (VI) in: - R a This indicates an aryl or heteroaryl group, wherein the heteroaryl and aryl groups are optionally substituted with at least one of the following groups: F, OH, C(O)OMe, NHC(O)Me, methyl (Me), CF3, OH, or SO2. - ; - Q represents Li, Na, K or Zn, with Na or K being preferred; - p means 1 or 2.

[0068] The compounds of formula (VI) may be selected from the following compounds: According to a preferred embodiment, the compound of formula (VI) is selected from the following compounds: The total content of the compound of formula (VI) as defined above may be from 0.05% to 10.0% by weight, preferably from 0.1% to 3.0% by weight, and even more preferably from 0.2% to 1.5% by weight, relative to the total weight of the crosslinkable two-component composition according to the invention.

[0069] (meth)acrylate compounds Component B may contain one or more (meth)acrylate compounds as defined for component A.

[0070] The (meth)acrylate compound of component B may be the same as or different from the (meth)acrylate compound of component A.

[0071] Preferably, component B comprises one or more (meth)acrylate compounds.

[0072] Relative to the total weight of component B, component B may contain more than 5% by weight of (meth)acrylate compound, preferably more than 20% by weight, and advantageously more than 50% by weight of compound M1, more preferably more than 70% by weight, and even more preferably more than 90% by weight.

[0073] Component B may contain, in particular, 60% to 99.9% by weight of (meth)acrylate compound, and preferably 80% to 99.5% by weight, relative to the total weight of component B.

[0074] Preferably, the (meth)acrylate compound of component B does not contain any acid groups. Acid groups can be phosphate groups, thiophosphate groups, phosphonic acid groups, sulfonic acid groups, and carboxylic acid groups. For example, the (meth)acrylate compound in component B is not 10-methacryloyloxydecyl dihydrophosphate.

[0075] Preferably, the (meth)acrylate compound of component B is not a compound of formula (V) as defined above.

[0076] Preferably, the (meth)acrylate compound of component B is selected from compounds of formula (I), (II) or (III) as defined above.

[0077] Composition The crosslinkable two-component composition according to the present invention may contain at least one additive selected from catalysts, fillers, antioxidants, polymerization inhibitors, light stabilizers / UV absorbers, metal passivators, antistatic agents, antifogging agents, foaming agents, biocides, plasticizers, lubricants, emulsifiers, dyes, pigments, rheology modifiers, impact modifiers, adhesion promoters, accelerators, fluorescent whitening agents, flame retardants, anti-seepage agents, nucleating agents, solvents, and mixtures thereof.

[0078] These additives may be present in component A and / or component B of the composition according to the invention.

[0079] As examples of plasticizers that can be used, any plasticizer commonly used in the field of adhesives may be mentioned, such as epoxy resins, phthalates, benzoates, trimethylolpropane, trimethylolethane, trimethylolmethane, glycerides, pentaerythritol esters, cycloalkane mineral oils, adipates, cyclohexyldicarboxylate, paraffin oils, natural oils (optionally epoxidized), polypropylene, polybutene, hydrogenated polyisoprene, and mixtures thereof.

[0080] For example, you can use: - Diisodecyl phthalate, for example, produced by BASF under the name Palatinol TM DIDP sales, - Esters of alkyl sulfonic acids and phenols, such as those marketed by Lanxess under the name Mesamoll®. - Diisononyl 1,2-cyclohexanedicarboxylate, which is marketed by BASF, for example, under the name Hexamoll Dinch®. - Pentaerythritol tetrapentarate, which, for example, is produced by Perstorp under the name Pevalen TM Sale, - Epoxidized soybean oil, which, for example, is sold by Arkema under the name Vikoflex® 7170.

[0081] As an example of a rheology (thixotropic) agent that can be used, any rheology agent conventionally used in the field of adhesive compositions may be mentioned.

[0082] Preferably, the thixotropic agent is selected from: - PVC plastisols, corresponding to PVC suspensions in plasticizers miscible with PVC, are obtained in situ by heating to a temperature of 60°C to 80°C. These plastisols may be those specifically described in the publication "Polyurethane Sealants," Robert M. Evans, ISBN 087762-998-6. - Fumed silica, which, for example, is sold by Wacker under the name HDK® N20; - Urea derivatives, which are produced by the reaction of an aromatic diisocyanate monomer, such as 4,4'-MDI, with an aliphatic amine, such as butylamine. The preparation of such urea derivatives is specifically described in patent application FR 1 591 172; - Micronized amide waxes, such as Crayvallac® SLT or Crayvallac® SLA sold by Arkema.

[0083] The compositions according to the present invention may further contain at least one organic filler and / or mineral filler.

[0084] Advantageously, the mineral fillers that can be used are selected in order to improve the mechanical properties of the compositions according to the invention in the crosslinked state.

[0085] Regarding the mineral fillers that can be used, any mineral filler commonly used in the field of adhesive compositions can be used. These fillers are typically in granular form with various geometries. For example, they can be spherical, fibrous, or irregularly shaped.

[0086] Preferably, the filler is selected from clay, quartz, carbonate filler, kaolin, gypsum, and mixtures thereof; preferably, the filler is selected from carbonate filler, such as alkali metal or alkaline earth metal carbonates, and more preferably calcium carbonate or chalk.

[0087] These fillers can be untreated or treated, for example, with organic acids such as stearic acid, or a mixture of organic acids consisting mainly of stearic acid.

[0088] Mineral hollow microspheres, such as glass hollow microspheres, can also be used, and more particularly those made of sodium calcium borosilicate or sodium calcium aluminosilicate.

[0089] The filler can be a conductive filler and / or a thermally conductive filler.

[0090] Among conductive fillers, examples include carbon black, graphite, carbon fiber, metal M' optionally coated with a metal M'' layer, mineral or organic fillers coated with a metal layer, and mixtures thereof.

[0091] Among metals coated with a metal layer, copper coated with a silver layer can be mentioned, for example.

[0092] Organic fillers can be coated with a metal such as silver or copper. For example, polymethyl methacrylate (PPMA) coated with silver can be mentioned.

[0093] Examples of thermally conductive fillers include, for example, carbon black powder, graphite, carbon fiber (CNT), metal oxides, metal hydroxides, metal silicates, metal sulfides, boron nitride, and aluminum nitride. The metal compounds are selected from, for example, tin, indium, antimony, aluminum, titanium, iron, magnesium, zinc, etc. Electrically conductive and / or thermally conductive fillers can be in the form of spherical particles, tubes, sheets, or fibers, particularly having a thickness of 0.01 μm. 2 / g to 100 m 2 Specific surface area per g.

[0094] Preferably, the composition comprises a conductive filler.

[0095] Relative to the total weight of the composition according to the invention, the composition may contain 0% to 95% by weight, and preferably 40% to 95% by weight, one or more conductive fillers and / or thermally conductive fillers.

[0096] Preferably, the conductive filler and / or the thermally conductive filler are in component B of the composition.

[0097] The compositions according to the invention may further contain at least one adhesion promoter, which is preferably selected from silanes, such as aminosilanes, epoxysilanes or acryloylsilanes.

[0098] When pigments are present in the composition, the pigment content is preferably less than or equal to 3% by weight, and more preferably less than or equal to 2% by weight, relative to the total weight of the composition. When pigments are present, the pigment content may be, for example, from 0.1% by weight to 3% by weight or from 0.4% by weight to 2% by weight, relative to the total weight of the composition.

[0099] Pigments can be inorganic or organic.

[0100] For example, the pigment is TiO2, particularly Kronos® 2059 sold by Kronos.

[0101] The composition may 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 caused by reaction with oxygen, which can be formed by heat or light. These compounds may include a primary antioxidant that scavenge free radicals. The primary antioxidant may be used alone or in combination with other secondary antioxidants or UV stabilizers.

[0102] Examples that may be mentioned include Irganox® 1010, Irganox® B561, Irganox® 245, Irgafos® 168, Tinuvin® 328, or Tinuvin, all sold by BASF. TM 770.

[0103] According to a preferred embodiment, the two-component composition according to the invention does not contain any peroxides.

[0104] According to a preferred embodiment, the two-component composition according to the invention does not contain any quaternary ammonium salt, such as dilauryl dimethyl ammonium chloride or dodecyl trimethyl ammonium chloride.

[0105] According to a preferred embodiment, the two-component composition according to the invention does not contain any aromatic amines.

[0106] According to a preferred embodiment, the two-component composition according to the invention does not contain any vanadium-based compounds.

[0107] In the composition according to the invention, the volume ratio of component A to component B can be from 20 / 1 to 1 / 1, preferably from 10 / 1 to 1 / 1. The volume ratio of A to B is preferably 1 / 1. Such a ratio is unpredictable in a peroxide / tertiary amine system.

[0108] B. Ready-to-use kit The invention also relates to ready-to-use kits comprising both component A as defined above and component B as defined above, packaged in two separate chambers. For example, this could be a two-component cartridge.

[0109] Specifically, the composition according to the invention can be, for example, in a two-component form within a ready-to-use kit, the ready-to-use kit containing both component A in a first chamber or container and component B in a second chamber or container, the ratio of which is suitable for direct mixing of the two components, for example, by means of a metering pump.

[0110] According to one embodiment of the invention, the kit further includes one or more means for mixing components A and B. Preferably, the mixing means is selected from metering pumps and static mixers, having a diameter suitable for the amount used.

[0111] C. Use of the composition The present invention also relates to the use of crosslinkable two-component compositions as defined above as adhesives, glues or coatings, preferably as adhesives.

[0112] The present invention also relates to the use of the composition as a structural or semi-structural adhesive for bonding and / or repairing materials in fields such as transportation, motor vehicles (cars, buses or trucks), assembly, marine, electronics or construction.

[0113] This invention relates to a method for assembling two substrates by bonding them together with an adhesive, the method comprising: - Mix components A and B as defined above to form a composition as defined above; - Coat at least one of the two substrates to be assembled with the composition; - Ensure effective contact between the two substrates; then - Crosslinked composition.

[0114] The crosslinking step can be carried out at a temperature between 0°C and 200°C, preferably between 10°C and 150°C, more preferably between 23°C and 80°C, and especially between 20°C and 25°C.

[0115] 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 such as PVC, polycarbonate, PMMA, polyethylene, polypropylene, polyester, epoxy resin; substrates made of metal and composite materials coated with paint.

[0116] Crosslinking can be performed, for example, using electromagnetic radiation from a UV radiation source or an LED. In the case of an opaque substrate, electromagnetic radiation can be performed at the bonding edge, or in the case of a transparent substrate, electromagnetic radiation can be performed directly through the substrate.

[0117] The crosslinking step under electromagnetic radiation can be carried out at wavelengths greater than 300 nm, preferably 360 nm to 680 nm, and even more preferably 360 nm to 420 nm.

[0118] The inventors have advantageously discovered that the opening time can be significantly altered by changing various parameters, such as the nature or content of organocopper derivatives and / or sulfinates and / or compounds of formula (X). The presence of photoinitiator P1 and / or exposure to electromagnetic radiation also advantageously allows for a reduction in the opening time.

[0119] Furthermore, the composition advantageously exhibits rapid cohesive build-up, independent of open time (short in the electronic field, or long in the wind field). Additionally, the composition according to the invention advantageously exhibits good adhesive properties and advantageously results in a non-sticky surface after adhesive bonding.

[0120] Compared to peroxide-based compositions, the compositions according to the invention are advantageously suited for transport.

[0121] The present invention also relates to a method for determining the crosslinking of a crosslinkable two-component composition as defined above, the method comprising the step of mixing components A and B as defined above.

[0122] The method of the present invention applies to all embodiments of the crosslinkable two-component composition and to components A and B as defined above.

[0123] The mixing process can take anywhere from 30 seconds to 1 minute.

[0124] During the initial mixing of components A and B, the composition advantageously colors, especially when the organocopper derivative is an organocopper(II) derivative, to a blue color; this particularly makes it possible to check that the mixture of parts A and B is homogeneous. During the crosslinking step, the composition advantageously changes color.

[0125] This color change in the composition advantageously allows for the monitoring and determination of when the composition polymerizes / crosslinks. This advantageous effect eliminates the need for additional colorants and allows for the verification of efficient mixing and effective polymerization / crosslinking through simple visual observation, thus benefiting end-user use.

[0126] All of the above embodiments can be combined with each other. In particular, various of the above-described components of the composition, and especially the preferred embodiments of the composition, can be combined with each other.

[0127] In the context of this invention, the term "between x and y" or "x to y" refers to a range that includes the limiting values ​​x and y. For example, the range "between 0% and 25%" specifically includes the values ​​0% and 25%.

[0128] The invention will now be described in the following embodiments, which are given by way of illustration only and should not be construed as limiting the scope of the invention. Example

[0129] Use the following ingredients: - SR® 531: Cyclic trimethylolpropane acetal acrylate sold by Arkema (CAS No.: 66492-51-1); - Cu(Acac)2: Copper(II) (acetylacetone) from Sigma-Aldrich (CAS No.: 13395-16-9); - Sodium p-toluenesulfinate from Sigma-Aldrich (CAS No.: 824-79-3); - Mixture G, which comprises bis[2-(methacryloyloxy)ethyl]phosphate and 2-(methacryloyloxy)ethyl phosphate; - MEP: Bis[2-(methacryloyloxy)ethyl] phosphate (CA: 32435-46-4) available from Sigma-Aldrich.

[0130] - EHP: Bis(2-ethylhexyl) phosphate (CAS: 298-07-7) available from Sigma-Aldrich; - HEMA: 2-Hydroxyethyl methacrylate; - MA: Methacrylic acid available from Sigma-Aldrich (CAS: 79-41-4); Visiomer® BNMA: Benzyl methacrylate sold by Evonik.

[0131] Example 1 Preparation of Composition No. 1 (according to the present invention) In a mixer with constant stirring and air, mix the components of component A in the proportions shown in the table below at a temperature of 23°C.

[0132] In a mixer with constant stirring and air, the various components constituting component B are mixed in the proportions shown in the table below at a temperature of 23°C.

[0133] [Table 1] Use the Sulzer® mixpac mixer to mix component A and component B at an ambient temperature of 23°C in a 1:1 volume ratio.

[0134] Adhesive bonding test: Composition 1 was deposited on a first glass microscope slide (25 × 76 mm) by mixing components A and B using a mixer (Sulzer® mixpac); - Attach the second glass microscope slide (25×76 mm) onto the first slide receiving composition 1; - Perform the step of sliding the two microscope slides so that composition 1 can be evenly distributed between the two slides (this reduces oxygen exposure).

[0135] The adhesive bonding time is the time after which the two slides can no longer be separated.

[0136] Finally, the adhesive bonding time was 30.0 minutes. The results favorably demonstrated good adhesion of Composition 1 without the use of aromatic amines or organic peroxides.

[0137] Example 2 Preparation of Composition No. 2 (according to the present invention) In a mixer with constant stirring and air, mix the components of component A in the proportions shown in the table below at a temperature of 23°C.

[0138] In a mixer with constant stirring and air, the various components constituting component B are mixed in the proportions shown in the table below at a temperature of 23°C.

[0139] [Table 2] Use the Sulzer® mixpac mixer to mix component A and component B at an ambient temperature of 23°C in a 1:1 volume ratio.

[0140] Example 3 Preparation of Composition No. 3 (according to the present invention) In a mixer with constant stirring and air, mix the components of component A in the proportions shown in the table below at a temperature of 23°C.

[0141] In a mixer with constant stirring and air, the various components constituting component B are mixed in the proportions shown in the table below at a temperature of 23°C.

[0142] [Table 3] Use the Sulzer® mixpac mixer to mix component A and component B at an ambient temperature of 23°C in a 1:1 volume ratio.

[0143] Example 4 Preparation of Composition No. 4 (according to the present invention) In a mixer with constant stirring and air, mix the components of component A in the proportions shown in the table below at a temperature of 23°C.

[0144] In a mixer with constant stirring and air, the various components constituting component B are mixed in the proportions shown in the table below at a temperature of 23°C.

[0145] [Table 4] Use the Sulzer® mixpac mixer to mix component A and component B at an ambient temperature of 23°C in a 1:1 volume ratio.

[0146] Example 5 Performance of Compositions No. 2, No. 3 and No. 4 Reactivity measurement: The exothermic reaction is continuously analyzed using a pyrometer and thermal imaging.

[0147] Peak time is the time required to reach the peak temperature (the maximum exothermic temperature observed during polymerization).

[0148] Time / temperature profiles were generated using an Omega OS552-V1-6 industrial infrared thermometer (Omega Engineering®, Inc., Stamford, CT), accurate to ±1°C for polymerization of 2 g (approximately 4.0 mm height) and 0.25 g (1.4 mm height).

[0149] The results are given in the table below: [Table 5] Example 6 Properties of the photoactivated composition No. 2 Photoactivation of composition 2 (Example 2) was performed during high-temperature measurement.

[0150] Photoactivation and reactivity assays: Photoactivation of a 395 nm LED lamp (power 1 W / cm²) attached to a pyrometer 2 The process is as follows: LED activation occurs within a maximum of 45 seconds, after which the peak heat release time is measured. The sample temperature immediately drops below 40°C after photoactivation.

[0151] The exothermic reaction is continuously analyzed using a pyrometer and thermal imaging.

[0152] Peak time is the time required to reach the peak temperature (the maximum exothermic temperature observed during polymerization).

[0153] Time / temperature profiles were generated using an Omega OS552-V1-6 industrial infrared thermometer (Omega Engineering®, Inc., Stamford, CT), accurate to ±1°C for polymerization of 2 g (approximately 4.0 mm height) and 0.25 g (1.4 mm height).

[0154] Component A and component B were mixed at a 1:1 volume ratio using a Sulzer® mixpac mixer at an ambient temperature of 23°C. The high-temperature measurement results are given in the table below: [Table 6] The results showed that composition 2 advantageously crosslinks without the use of aromatic amines, peroxides, or halogenated compounds. Composition 2 advantageously crosslinks with or without photochemical radiation (UV radiation). With UV radiation, the peak time advantageously decreases with the radiation dose, indicating that the crosslinking rate increases with increasing dose. The crosslinking rate can advantageously be controlled by the radiation dose.

Claims

1. A crosslinkable two-component composition comprising: - Component A, which comprises: Organocopper derivatives; At least one (meth)acrylate compound; Compounds of formula (X): P(O)(OR) b (OR) c (OR) d ), where R b R c R d They may be the same or different, and are selected from hydrogen, alkyl, aryl, heteroaryl, alkenyl, cycloalkyl, wherein the alkyl, aryl, heteroaryl, alkenyl, and cycloalkyl groups may optionally be substituted; - Component B, which comprises: - At least one compound having the following formula (VI): in: - R a This indicates an aryl or heteroaryl group, wherein the heteroaryl and aryl groups are optionally substituted with at least one of the following groups: F, OH, C(O)OMe, NHC(O)Me, methyl (Me), CF3, OH, or SO2. - ; - Q represents Li, Na, K or Zn, with Na or K being preferred; - p indicates 1 or 2; - Optional at least one (meth)acrylate compound; The crosslinkable two-component composition is characterized in that the total content of the compound of formula (X) is from 0.1% to 20% by weight relative to the total weight of the composition.

2. The composition according to claim 1, characterized in that The organocopper derivative is selected from copper salts of formula (VII-1) or copper complexes of formula (VII-2): in: - R and R'' independently represent alkyl, cycloalkyl, aryl or heteroaryl, wherein the alkyl, cycloalkyl, aryl and heteroaryl are optionally substituted by one or more halogen atoms, for example by one or more fluorine atoms; - R' represents a hydrogen atom, alkyl, cycloalkyl, aryl, or heteroaryl group. Alternatively, R and R' (or R' and R'') can be attached to the same ring containing 5 to 8 carbon atoms, which may optionally contain at least one heteroatom (e.g., O or S); - R''' represents alkyl, cycloalkyl, aryl, or heteroaryl, wherein the alkyl, cycloalkyl, aryl, or heteroaryl group is optionally substituted with one or more halogen atoms, for example, with one or more fluorine atoms.

3. The composition according to any one of claims 1 and 2, characterized in that The organocopper derivative is a copper salt of formula (VII-2), preferably copper acetylacetonate (II)(Cu(acac)2).

4. The composition according to any one of claims 1 to 4, characterized in that The organocopper derivative of component A is unhalogenated.

5. The composition according to any one of claims 1 to 4, characterized in that The (meth)acrylate compound is a (meth)acrylate monomer, a (meth)acrylate oligomer, or a (meth)acrylate polymer.

6. The composition according to any one of claims 1 to 5, characterized in that The (meth)acrylate compound has the following formula (F): in: - R 1 Indicates H or methyl; - G represents an organic group, which is preferably selected from alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkylaryl, arylalkyl or aryl, wherein the alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkylaryl, arylalkyl and aryl groups may optionally be substituted with, for example, alkyl or hydroxyl groups.

7. The composition according to any one of claims 1 to 6, characterized in that The (meth)acrylate compound has one of the following formulas (I), (II), (III), (IV) or (V): in: - R 1 Indicates H or methyl; - R 2 Indicates H, methyl, or ethyl; - p represents 0 or 1; and - Z represents H, O, S, alkyl, benzyl, aryl, or alkoxy; - Y represents O, S, NH or CH2; - Is it a single or double bond? The condition is that when Z represents O, then the key... It is a double bond; - G' is selected from alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkylaryl, arylalkyl or aryl, wherein the alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkylaryl, arylalkyl and aryl groups are optionally substituted with alkyl groups, and the group G' is characterized in that it does not contain heteroatoms; - G'' is an alkyl group substituted with an OH group.

8. The composition according to any one of claims 1 to 7, characterized in that: - The compound of formula (I) is selected from methyl methacrylate, 2-ethylhexyl methacrylate, n-butyl methacrylate, heptyl methacrylate, 2-tert-butylheptyl methacrylate, octyl methacrylate, 3-isopropylheptyl methacrylate, nonyl methacrylate, decyl methacrylate, undecyl methacrylate, 5-methylundecyl methacrylate, dodecyl methacrylate, 2-methyldodecyl methacrylate, tridecyl methacrylate, 5-methyltridecyl methacrylate, tetradecyl methacrylate, pentadecyl methacrylate, hexadecyl methacrylate, and so on. 2-Methylhexadecyl methacrylate, heptadecanyl methacrylate, 5-isopropylheptadecanyl methacrylate, 4-tert-butyloctadecyl methacrylate, 5-ethyloctadecyl methacrylate, 3-isopropyloctadecyl methacrylate, octadecyl methacrylate, nonadecanyl methacrylate, eicosyl methacrylate, borneol methacrylate, 2,3,4,5-tetra-tert-butylcyclohexyl methacrylate; benzyl methacrylate, phenyl methacrylate, 2-(2-ethoxyethoxy)ethyl methacrylate, 2-phenoxyethyl methacrylate, isoborneol methacrylate, and mixtures thereof. - The compounds of formula (II) are selected from the following monomers: - The compounds of formula (III) are selected from the following monomers: - The compounds of formula (V) are selected from hydroxyethyl methacrylate and hydroxypropyl methacrylate.

9. The composition according to any one of claims 1 to 8, characterized in that The (meth)acrylate compounds are selected from: benzyl (meth)acrylate, hydroxyethyl (meth)acrylate, compound (III-F), compound (II-A), compound (III-A), and mixtures thereof.

10. The composition according to any one of claims 1 to 9, characterized in that The compounds of formula (VI) are selected from the following compounds: The compounds of formula (VI) are preferably selected from the following compounds: 。 11. The composition according to any one of claims 1 to 10, characterized in that The compound of formula (X) is wherein R b R c and R d At least one of the compounds that represent hydrogen.

12. The composition according to any one of claims 1 to 11, characterized in that The compound of formula (X) is selected from phosphoric acid, 2-(methacryloyloxy)ethyl phosphate, bis[2-(methacryloyloxy)ethyl] phosphate, 2-(acryloyloxy)ethyl phosphate, bis[2-(acryloyloxy)ethyl] phosphate, (2-ethylhexyl) phosphate, bis(2-ethylhexyl) phosphate, and mixtures thereof.

13. The composition according to any one of claims 1 to 12, characterized in that The compound of formula (X) is selected from bis[2-(methacryloyloxy)ethyl] phosphate, bis(2-ethylhexyl) phosphate and mixtures thereof.

14. The composition according to any one of claims 1 to 13, characterized in that It does not contain any peroxides.

15. The composition according to any one of claims 1 to 14, characterized in that It does not contain any aromatic amines.

16. The composition according to any one of claims 1 to 15, characterized in that It does not contain any vanadium-based compounds.

17. A ready-to-use kit comprising both component A as claimed in any one of claims 1 to 16 and component B as claimed in any one of claims 1 to 16, packaged in two separate compartments.

18. Use of the crosslinkable two-component composition as an adhesive, glue, or coating as claimed in any one of claims 1 to 16, preferably as an adhesive.

Images