FR3140375A1 - Two-component composition comprising an organoborane-amine complex - Google Patents

Abstract

The invention relates to a two-component composition comprising: - a component A comprising: - an organoborane-amine complex, and - a polymer polyol having a number average molar mass of less than 4500 g/mol; and - a component B comprising: - a polymer comprising at least one acrylic group and at least one isocyanate group; the component A and/or the component B further comprising at least one acrylic monomer and/or polymer. The invention also relates to the use of the two-component composition according to the invention and an article comprising the two-component composition according to the invention. Figure: none

Description

Two-component composition comprising an organoborane-amine complex Field of the invention

The present invention relates to a two-component composition comprising an organoborane-amine complex, its use and an article comprising it.

Technical background

The nature of the surface of a substrate can be characterized by its surface energy. Low surface energy substrates, such as polyolefins (like polypropylene) or fluoropolymers (like polyvinylidene fluoride (PVDF)), are known to be difficult to bond to each other or to other types of substrates and often require surface treatment before bonding. This is because they have very few binding sites available on their free surface. These treatments, such as plasma or corona treatment, abrasion or treatment with a chemical agent, consist of chemically and/or physically modifying the surface of the substrate to favorably modify its surface energy.

However, this type of treatment has a certain number of disadvantages, such as a high process cost, results that are not necessarily reproducible, as well as an effect that diminishes over time.

Recently, it has been discovered that the use of adhesive compositions comprising organoboranes makes it possible to improve the adhesion of compounds that can be polymerized by radical means on low energy surfaces. However, due to the unstable and pyrophoric nature of organoboranes, they must be complexed with an amine in order to avoid oxidative decomposition. Thus, when using this type of composition, a decomplexing agent releases the organoborane from the amine, so that it can initiate the polymerization of a radically polymerizable compound present in the composition. This type of composition is often in the form of two parts (one comprising the organoborane-amine complex and one comprising the decomplexing agent) mixed just before use and application of the composition. The radically polymerizable compound may be present in at least one of the two compositions.

Generally speaking, the decomplexing agent can react with the amine of the organoborane-amine complex to release the organoborane which can then initiate the polymerization of the polymerizable compound. Thus, after crosslinking, the two-component composition comprises a first type of compound, that is to say the decomplexing agent having reacted with the amine, and a second type of compound, that is to say the polymer formed at from the polymerizable compound. Consequently, the polymer network of the crosslinked composition is not homogeneous and presents a certain fragility which can influence the adhesive properties of the composition.

Furthermore, battery cells are generally obtained by mixing in particular an electroconductive filler (such as carbon black) with PVDF and using an organic solvent such as N-methyl-2-pyrrolidone (NMP) in order to ensure a cohesion between these components. However, NMP poses ecological problems and manufacturers are seeking to replace it.

There is therefore a need to provide a composition having improved adhesion properties (in particular higher shear strength), in particular for substrates having low surface energy, the crosslinked composition being homogeneous.

There is also a need to provide a composition that can be used as a binder in a battery cell, in order to replace the organic solvent such as NMP generally used.

The invention relates to a two-component composition comprising:

- a component A comprising:
- an organoborane-amine complex, and
- a polymer polyol having a number average molar mass of less than 4500 g/mol; And

- a component B comprising:
- a polymer comprising at least one acrylic group and at least one isocyanate group;

the component A and/or the component B further comprising at least one acrylic monomer and/or polymer.

The invention also relates to the use of the two-component composition according to the invention, as an adhesive and/or binder, as a coating or as a primer.

Finally, the invention relates to an article, in particular a battery cell, comprising the two-component composition according to the invention.

Surprisingly, it was found that the two-component composition according to the invention, comprising in particular a polyol polymer having a number average molar mass of less than 4500 g/mol, has improved adhesion properties (in particular shear resistance). for a low surface energy substrate. In addition, the two-component composition according to the invention is homogeneous after crosslinking.

In addition, the two-component composition according to the invention can be used as a binder in a battery cell, without the need to use an NMP type solvent.

Description of the invention

The invention relates to a two-component composition comprising:

- a component A comprising:
- an organoborane-amine complex, and
- a polymer polyol having a number average molar mass of less than 4500 g/mol; And

- a component B comprising:
- a polymer comprising at least one acrylic group and at least one isocyanate group;

the component A and/or the component B further comprising at least one acrylic monomer and/or polymer.

Organoborane-amine complex

Component A comprises an organoborane-amine complex, that is, a complex of organoborane with an amine.

Organoborane

By “organoborane” is meant a compound comprising at least one boron atom linked to at least one carbon atom.

The organoborane can be of formula (I):

in which R, R' and R'', identical or different, each represent a hydrogen atom or a hydrocarbon group comprising from 1 to 20 carbon atoms, with a linear or branched open chain, or comprising one or more optionally aromatic rings , preferably from 1 to 10 carbon atoms, more preferably from 1 to 5 carbon atoms. Said hydrocarbon group may optionally comprise one or more heteroatoms (such as nitrogen, oxygen, sulfur, halogen, etc.). Preferably, R, R’ and R’’, identical or different, each represent a hydrocarbon group as described above.

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

According to one embodiment, R, R' and R'', identical or different, each represent a hydrocarbon group chosen from methyl, ethyl, n-propyl, iso-propyl, cyclopropyl, tert-butyl, iso-butyl, n- butyl, sec-butyl, cyclobutyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, an alkyl substituted by an aryl (such as a phenyl), a phenyl substituted or not by one or more groups such as an alkyl, a cycloalkyl, an alkoxy, a halogen, a nitro group and/or a carbonyl group, a naphthyl substituted or not by one or more groups such as an alkyl, a cycloalkyl, an alkoxy, a halogen, a nitro group and/or a carbonyl group, a heteroaryl substituted or not by one or more groups such as an alkyl, a cycloalkyl, an alkoxy, a halogen, a nitro group and/or a carbonyl group. As examples of heteroaryl groups, mention may be made of pyridines, pyrroles, carbazoles, imidazoles, furans, pyrans and thiophenes. Alternatively, two of R, R’ and R’’ can be part of the same cycle.

Advantageously, R, R' and R'', identical or different, preferably identical, each represent an alkyl group, preferably an alkyl group having from 1 to 5 carbon atoms, in particular chosen from methyl, ethyl, n-propyl, isopropyl, cyclopropyl, tert-butyl, iso-butyl, n-butyl, sec-butyl, cyclobutyl, n-pentyl and cyclopentyl, in particular from ethyl, n-butyl and sec-butyl.

According to a preferred embodiment, R, R’ and R’’ are identical. Preferably, R, R' and R'' are ethyl, n-butyl, or sec-butyl groups, more preferably ethyl. Thus, the organoborane is preferably triethylborane, tri-n-butylborane or tri-sec-butylborane, more preferably triethylborane.

Since organoborane is a highly reactive molecule, its complexation with an amine is necessary to prevent its decomposition and to allow its conservation.

Amine

The amine can be a monoamine (comprising a single amine group) or a polyamine (comprising at least two amine groups), preferably a polyamine.

When the amine is a monoamine, it can be a primary, secondary or tertiary monoamine.

According to one embodiment, the monoamine has formula (II):

in which R ¹ , R ² and R ³ , identical or different, each represent a hydrogen atom or a hydrocarbon group comprising from 1 to 20 carbon atoms. This hydrocarbon group may be saturated or unsaturated, with a linear or branched open chain, or comprise one or more possibly aromatic rings.

According to one embodiment, R ¹ , R ² and R ³ , identical or different, each represent a hydrogen atom or a hydrocarbon group chosen from methyl, ethyl, n-propyl, iso-propyl, cyclopropyl, tert-butyl, iso-butyl, n-butyl, sec-butyl, cyclobutyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, an alkyl substituted by an aryl (such as phenyl), a phenyl substituted or not by one or more groups such as an alkyl, a cycloalkyl, an alkoxy, a halogen, a nitro group and/or a carbonyl group, a naphthyl substituted or not by one or more groups such as an alkyl, a cycloalkyl, an alkoxy, a halogen, a nitro group and/or a carbonyl group, a heteroaryl substituted or not by one or more groups such as an alkyl, a cycloalkyl, an alkoxy, a halogen, a nitro group and/or a carbonyl group. Examples of heteroaryl groups include pyridines, pyrroles and carbazoles. Alternatively, two of R ¹ , R ² and R ³ can be part of the same cycle, for example a pyrrolidine, a piperidine, a morpholine, a thiomorpholine, or even several cycles, for example 1-azabicyclo[2.2.2]octane (or quinuclidine).

Preferably, when the amine is a monoamine, it is chosen from tert-butylamine, 3-methoxypropylamine, diisopropylamine, diethylamine, triethylamine and diethylaniline, in particular 3-methoxypropylamine.

According to another embodiment, the monoamine is a polyetheramine, that is to say an amine comprising several ether functions.

The polyetheramine can be of formula (II’):

in which :

- R ⁴ , R ⁵ and R ¹⁰ , identical or different, each represent a hydrogen atom or a group comprising 1 to 10 carbon atoms, linear or branched, saturated or unsaturated.

- R ¹ and R ² are as described above;

- t, x and y, identical or different, each represent a number from 0 to 70, preferably from 0 to 50, more preferably from 0 to 30, at least one of the numbers t, x and/or y being different from 0.

Preferably, R ⁴ , R ⁵ and R ¹⁰ , identical or different, each represent a group comprising from 1 to 10 carbon atoms, preferably from 1 to 7 carbon atoms and more preferably from 1 to 3 linear carbon atoms or branched. More preferably, R ⁴ , R ⁵ and R ¹⁰ , identical or different, each represent an alkyl group, in particular a methyl or ethyl group.

The numbers t, x and y can be integers or not. For example, if a mixture of different alkylene oxides is used, t corresponds to the average degree of ethoxylation of the ethoxy groups substituted by an R ¹⁰ group.

The monoamines of formula (II') can have a molecular mass of 200 to 5500 g/mol, and preferably of 500 to 2500 g/mol.

This type of polyetheramines is for example marketed under the name “ Jeffamine series M ” by the company HUNTSMAN.

When the amine is a polyamine, it comprises at least two amine groups which may be of primary, secondary and/or tertiary type.

Polyamines comprising more than two amine groups (for example three or four) such as polyethyleneimines (also called polyaziridines) can be used, such as tetraethylenepentamine, as well as polyethyleneimines marketed under the name EPOMIN (in particular EPOMIN SP-012) by the company NIPPON SHOKUBAI, or LUPASOL® (in particular LUPASOL® FG) by the company BASF.

Preferably, the polyamine is a primary polyamine, that is to say that all of its amine groups are primary, more preferably the polyamine is a primary diamine.

For example, the polyamine can be of formula (III):

in which :

- R ⁶ represents a saturated or unsaturated divalent group comprising from 2 to 60 carbon atoms, preferably from 2 to 40 carbon atoms, more preferably from 2 to 15 carbon atoms, and

- R ⁱ , R ⁱⁱ , R ⁱⁱⁱ and R ^iv , identical or different, each represent a hydrogen atom or a hydrocarbon group, saturated or unsaturated, comprising from 1 to 20 carbon atoms, which may be aliphatic with a linear open chain or branched, or which may include one or more possibly aromatic rings.

In addition, R ⁶ represents a divalent group which may be aliphatic with a linear or branched open chain, or which may comprise one or more possibly aromatic rings, and optionally comprising one or more heteroatoms, preferably at most a single heteroatom, such as oxygen, sulfur , nitrogen and or halogen.

Preferably, R ⁶ is an alkyl group.

According to one embodiment, R ⁱ , R ⁱⁱ , R ⁱⁱⁱ and R ^iv , identical or different, each represent a hydrogen atom or a hydrocarbon group chosen from methyl, ethyl, n-propyl, iso-propyl, cyclopropyl, tert -butyl, iso-butyl, n-butyl, sec-butyl, cyclobutyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, an alkyl substituted by an aryl (such as phenyl), a phenyl substituted or not by an or several groups such as an alkyl, a cycloalkyl, an alkoxy, a halogen, a nitro group and/or a carbonyl group, a naphthyl substituted or not by one or more groups such as an alkyl, a cycloalkyl, an alkoxy, a halogen, a nitro group and/or a carbonyl group, a heteroaryl substituted or not by one or more groups such as an alkyl, a cycloalkyl, an alkoxy, a halogen, a nitro group and/or a carbonyl group. Examples of heteroaryl groups include pyridines, pyrroles and carbazoles. Alternatively, R ⁱ and R ⁱⁱ and/or R ⁱⁱⁱ and R ^iv can be part of the same cycle, for example of a pyrrolidine, a piperidine, a morpholine, a thiomorpholine.

According to a preferred embodiment, R ⁱ and R ⁱⁱ and/or R ⁱⁱⁱ and R ^iv are all hydrogen atoms.

Preferably, the polyamine is chosen from ethylenediamine, 1,3-propanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,12-dodecanediamine, 2-methyl-1,5-pentanediamine , 3-methyl-1,5-pentanediamine, isophoronediamine, 4,4'-methylenedianiline, 2-methylbenzene-1,4-diamine, diethylenetriamine, 4,6-diethyl-2-methylbenzene-1, 3-diamine, 4,4'-methylenebis(cyclohexylamine), 2,4,6-trimethyl-1,3-phenylenediamine, naphthalene-1,8-diamine.

More preferably, the polyamine is chosen from ethylenediamine, 1,3-propanediamine and 1,6-hexanediamine, even more preferably from 1,3-propanediamine and 1,6-hexanediamine, in particular 1,3- propanediamine.

A polyamine of the polyetheramine type comprising two amine groups, preferably primary, can alternatively be used.

The polyetheramine may comprise two amine groups, preferably primary, and one or more divalent ethoxy (–OCH ₂ CH ₂ –), propoxy (–OCH ₂ CH(CH ₃ )–) and/or butoxy (–OCH ₂ CH( CH ₂ CH ₃ )–), preferably ethoxy and/or propoxy. This type of polyetheramine is for example marketed under the name “ Jeffamine series D ”, “ Jeffamine series SD ” and “ Jeffamine series ED ” by the company HUNTSMAN.

The polyetheramine may comprise two amine groups and a divalent ethylenedioxy unit (–OCH ₂ CH ₂ O–), such as 2,2'-(ethylenedioxy)diethylamine. This type of polyetheramine is for example marketed under the name “ Jeffamine series EDR ” by the company HUNTSMAN.

The polyetheramine may comprise three amine groups, preferably primary, and one or more divalent ethoxy (–OCH ₂ CH ₂ –), propoxy (–OCH ₂ CH(CH ₃ )–) and/or butoxy (–OCH ₂ CH( CH ₂ CH ₃ )–), preferably propoxy. This type of polyetheramine is for example marketed under the name “ Jeffamine series T ” by the company HUNTSMAN.

The organoborane/amine molar ratio in the organoborane-amine complex can vary from 0.1 to 10, preferably from 0.5 to 5, more preferably from 0.5 to 2. This molar ratio is advantageously chosen so as to be approximately equal to the number of amine groups of the amine used in said complex. For example, when the amine is a monoamine, this ratio is preferably approximately 1. On the other hand, when the amine is a diamine, this ratio is preferably approximately 2.

By “approximately X”, we are aiming for more or less 10% of the value of X.

According to a preferred embodiment, the organoborane-amine complex can be chosen from triethylborane-1,3-propanediamine, tri-n-butylborane-3-methoxypropylamine, triethylborane-diethylenetriamine, tri-n-butylborane-1, 3-propanediamine, tri-sec-butylborane-1,3-propanediamine and triethylborane-1,6-hexanediamine, in particular triethylborane-1,3-propanediamine.

The content of organoborane-amine complex in component A can range from 2% to 70% by weight relative to the total weight of component A, preferably from 3% to 50% by weight, more preferably from 4% to 30% by weight. weight, even more preferably from 5% to 15% by weight.

In the context of the invention, the ranges of values are understood to be inclusive. For example, the range “between 0% and 25%” includes in particular the values 0% and 25%.

The organoborane included in the organoborane-amine complex can initiate radical polymerization after having been activated, that is to say decomplexed from the amine.

Polyol polymer

Component A comprises a polymer polyol having a number average molar mass of less than 4500 g/mol, preferably between 500 g/mol and 4000 g/mol, more preferably between 1000 g/mol and 3500 g/mol.

In the present application, the number average molecular mass of a polymer can be measured by methods well known to those skilled in the art, for example by gel permeation chromatography (GPC) using polystyrene type standards.

By “polymer” is meant a molecule comprising one or more repeated units.

By “polyol” is meant a molecule comprising at least two hydroxyl groups (–OH).

The polymer polyol, preferably polymer diol, may be chosen from polyether polyols, polyester polyols, polyolefin polyols, fluoropolymer polyols, polyene polyols, polycarbonate polyols, polycarbonate polyester polyols and mixtures thereof, preferably from polyene polyols, polycarbonate polyester polyols and their mixtures, more preferably among polyene polyols.

The polyether polyols may be polyoxyethylene polyols and/or polyoxypropylene polyols.

Polyester polyols can be polyester polyols of natural origin derived from castor oil and/or polyester polyols resulting from polycondensation:
- one or more aliphatic (linear, branched or cyclic) or aromatic polyols such as for example monoethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, butenediol, 1,6-hexanediol, cyclohexane dimethanol, tricyclodecane dimethanol, neopentyl glycol, cyclohexane dimethanol, glycerol, trimethylolpropane, 1,2,6-hexanetriol, sucrose, glucose, sorbitol, pentaerythritol, mannitol, N-methyldiethanolamine, triethanolamine, a dimeric fatty alcohol, a trimer fatty alcohol and mixtures thereof, with
- one or more polycarboxylic acids or its ester or anhydride derivative such as 1,6-hexanedioic acid, dodecanedioic acid, azelaic acid, sebacic acid, 1,18-octadecanedioic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, a dimeric fatty acid, a trimer fatty acid and mixtures of these acids, an unsaturated anhydride such as for example maleic or phthalic anhydride, or a lactone such as for example caprolactone.

By “polyolefin polyols”, we mean saturated aliphatic polymers resulting from the polymerization of an alkene and comprising at least two hydroxyl groups. The polyolefin polyols may be polyethylene polyols, polypropylene polyols, ethylene-propylene polyol copolymers, polybutene polyols, polyisobutylene polyols and/or polymethylpentene polyols.

The fluoropolymer polyols may be poly(vinylidene fluoride) polyols, poly(vinyl fluoride) polyols and/or polytetrafluoroethylene polyols.

By “polyene polyols” we mean polymers comprising at least two carbon-carbon double bonds and at least two hydroxyl groups. The polyene polyols may be polyisoprene polyols, polybutadiene polyols, polyfarnesene polyols and/or polydicyclopentadiene polyols, preferably polybutadiene polyols and/or polyfarnesene polyols.

Polycarbonate polyols can be obtained by reaction of carbonic acid derivatives, such as diphenyl carbonate, dimethyl carbonate or phosgene, with polyols, such as ethylene glycol, 1,2-propanediol, 1 ,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, 1,4-bis(hydroxymethyl)cyclohexane, 2 -methyl-1,3-propanediol, 2,2,4-trimethylpentane-1,3-diol, bisphenol A and/or tetrabromobisphenol A.

Polycarbonate polyester polyols can be obtained by reaction of polyols (in particular the polyols described above for obtaining polycarbonate polyols, in particular 1,6-hexanediol) with lactones (in particular based on caprolactone, in particular ε-caprolactone), followed by reaction of the resulting polyester polyols with carbonic acid derivatives, such as diphenyl carbonate, dimethyl carbonate or phosgene.

The polymer polyol content in component A can range from 20% to 98% by weight relative to the total weight of component A, preferably from 35% to 97% by weight, more preferably from 55% to 96% by weight, even more preferably from 65% to 95% by weight.

Polymer comprising at least one acrylic group and at least one isocyanate group

Component B comprises a polymer comprising at least one acrylic group and at least one isocyanate group (–NCO).

By “acrylic group” we mean in particular a group of formula (IX): -X-(C=O)-C(R ^V )=CH ₂ , in which R ^V represents a hydrogen atom or a methyl radical, preferably a hydrogen atom, and –X– represents –O– or –NR' ^N – with R' ^N representing a hydrogen atom or a linear or branched alkyl radical comprising from 1 to 22 carbon atoms, preferably from 1 to 18, more preferably from 1 to 14, even more preferably from 1 to 8 carbon atoms. Preferably, –X– represents –O–.

According to one embodiment, the isocyanate group(s) are present at the ends of the main chain of the polymer, and the acrylic group(s) are present in the form of lateral groups along the main chain and/or at the ends of the main chain. polymer. In particular, the isocyanate and acrylic groups are present at the ends of the polymer, that is to say at the ends of the main chain of the polymer.

The polymer comprising at least one acrylic group and at least one isocyanate group may have a number average molecular mass (Mn) of 500 to 50,000 g/mol.

According to a preferred embodiment, said polymer is a polyurethane, thus the polyurethane comprises at least one acrylic group and at least one isocyanate group.

According to a first embodiment, this polyurethane can be obtained according to the two-step process described in application WO 2017/108531. Thus, this polyurethane can be obtained by reaction of a hydroxylated polyether-acrylate, a hydroxylated polyester-acrylate or a hydroxylated polycarbonate-acrylate and at least one polyisocyanate.

According to a second embodiment which is preferred, this polyurethane can be obtained according to the two-step process described in document WO 2019/011784. Thus, this polyurethane can be obtained by reaction of a polyurethane comprising at least two terminal -NCO functions (preferably at the ends of the main chain), and at least one compound chosen from a hydroxylated ester of the acid (meth )acrylic and a hydroxylated amide of (meth)acrylic acid, preferably a hydroxylated ester of (meth)acrylic acid.

The term “ hydroxylated ester of (meth)acrylic acid ” means an ester of acrylic acid or methacrylic acid whose ester radical is substituted by at least one hydroxyl group. We can for example represent a hydroxylated ester of (meth)acrylic acid by the following formula: CH ₂ =C(R ^V )-C(=O)-OR ^O , in which R ^V is as described above , and R ^O represents an organic radical substituted by at least one hydroxyl group.

The hydroxylated ester of (meth)acrylic acid may have the following formula (X):

(X) CH ₂ =CR ^V -C(=O)-OR ^AC -OH

in which :

- R ^V is as described above, and

- R ^AC represents a saturated or unsaturated divalent hydrocarbon radical, aliphatic with a linear or branched open chain, or comprising one or more cycles, and optionally comprising one or more heteroatoms (such as N, O, S, in particular O).

R ^AC may optionally comprise one or more divalent groups chosen from -C(=O)O-, -C(=O)NH-, -NHC(=O)O-, -NHC(=O)-NH-, - C(=O)- and -N(R'' ^N )- with R'' ^N representing a linear or branched alkyl radical comprising from 1 to 22 carbon atoms.

Preferably, the hydroxylated ester of (meth)acrylic acid has one of the following formulas:

(X-1) CH ₂ =CR ^V -C(=O)-OR ^AC1 -OH,

(X-2) CH ₂ =CR ^V -C(=O)-OR ^AC1 -O-[C(=O)-(CH ₂ ) _r -O] _s -H, or

(X-3) CH ₂ =CR ^V -C(=O)-O-[R ^AC2 -O] _p -H

in which :

- R ^V is as described above,

- R ^AC1 represents a divalent hydrocarbon radical comprising from 2 to 22 carbon atoms, saturated or unsaturated, aliphatic with linear or branched open chain, or comprising one or more cycles, preferably from 2 to 18 carbon atoms, more preferably from 2 with 14 carbon atoms, even more preferably from 2 to 6 carbon atoms,

- r is an integer ranging from 1 to 10, preferably from 1 to 5, more preferably equal to 5,

- s is an integer ranging from 1 to 10, preferably equal to 2,

- R ^AC2 represents a linear or branched divalent hydrocarbon radical comprising from 2 to 4 carbon atoms, and

- p is an integer ranging from 2 to 120, preferably from 1 to 10, more preferably equal to 2 or 3.

As examples of hydroxylated esters of (meth)acrylic acid of formula (X-1), mention may be made of 2-hydroxyethyl acrylate (HEA), 2-hydroxypropyl acrylate (HPA), 2-hydroxybutyl acrylate (2- HBA), 4-hydroxybutyl acrylate (4-HBA), 2-hydroxyethyl methacrylate (HEMA), 2-hydroxypropyl methacrylate (HPMA), 2-hydroxybutyl methacrylate (2-HBMA), and 4-hydroxybutyl methacrylate (4 -HBMA).

As examples of hydroxylated esters of (meth)acrylic acid of formula (X-2), mention may be made of polycaprolactone acrylate SR 495B (CAPA) from SARTOMER or hydroxyethylcaprolactone acrylate (HECLA) from BASF.

As examples of hydroxylated esters of (meth)acrylic acid of formula (X-3), mention may be made of BLEMMER ® AP-150, BLEMMER ® AP-200, BLEMMER ® AP-400, BLEMMER ® AP -550, BLEMMER ® AP-800, BLEMMER ® AP-1000, BLEMMER ® AE-90, BLEMMER ® AE-150, BLEMMER ® AE-200, BLEMMER ® AE-350, BLEMMER ® AE- 400, marketed by NIPPON OIL & FATS CORPORATION, or SR 604 marketed by SARTOMER.

More preferably, the hydroxylated ester of (meth)acrylic acid is of formula (X-1), even more preferably chosen from 2-hydroxyethyl(meth)acrylate and 2-hydroxypropyl(meth)acrylate, in particular 2-hydroxyethyl(meth)acrylate.

The term “ hydroxylated amide of (meth)acrylic acid ” means an amide of acrylic acid or methacrylic acid whose amide radical is substituted by at least one hydroxyl group. We can for example represent a hydroxylated amide of (meth)acrylic acid by the formula: CH ₂ =CR ^V -C(=O)-N(R' ^N )-R ^N , in which R ^V and R' ^N are as described above and R ^N represents an organic radical substituted by at least one hydroxyl group.

The hydroxylated amide of (meth)acrylic acid can have the following formula (XI):

(XI) CH ₂ =CR ^V -C(=O)-N(R' ^N )-R ^AC -OH

in which R ^V , R' ^N and R ^AC are as described above.

Preferably, the hydroxylated amide of (meth)acrylic acid has one of the following formulas:

(XI-1) CH ₂ =CR ^V -C(=O)-N(R' ^N )-R ^AC3 -OH

(XI-2) CH ₂ =CR ^V -(=O)-N(R' ^N )-R ^AC3 -O-[C(=O)-(CH ₂ ) _r -O] _s -H

(XI-3) CH ₂ =CR ^V -C(=O)-N(R' ^N )-[R ^AC2 -O] _p -H

in which R ^V , R' ^N , r, s, R ^AC2 and p are as described above, and R ^AC3 represents a divalent hydrocarbon radical comprising from 1 to 22 carbon atoms, saturated or unsaturated, aliphatic with open chain linear or branched, or comprising one or more cycles, preferably from 1 to 14 carbon atoms, more preferably from 1 to 6 carbon atoms.

More preferably, the hydroxylated amide of the (meth)acrylic acid is of formula (XI-1), even more preferably chosen from 2-hydroxyethyl (meth)acrylamide and 2-hydroxypropyl (meth)acrylamide.

Alternatively, the hydroxylated ester or the hydroxylated amide may comprise more than one acrylic function and/or more than one hydroxyl function, such as glycerol monoacrylate, trimethylolpropane diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate and di- pentaerythritol pentacrylate.

Preferably, the polyurethane comprising at least one acrylic group and at least one isocyanate group is prepared by a process comprising the following steps:
- E1) the preparation of a polyurethane comprising at least two terminal NCO functions (preferably at the ends of the main chain) by a polyaddition reaction:
- i) at least one polyisocyanate, preferably chosen from diisocyanates, triisocyanates, diisocyanate oligomers and mixtures thereof,
- ii) with at least one polyol, preferably chosen from polyether polyols, polyester polyols, polyene polyols, polycarbonate polyols, poly(ether-carbonate) polyols, polymers with -OH endings and their mixtures,
in quantities such that the NCO/OH molar ratio, denoted (r1), is strictly greater than 1.0, preferably ranges from 1.60 to 1.90, and preferably ranges from 1.65 to 1.85; And
- E2) the reaction of the product formed at the end of step E1) with at least one hydroxylated ester of (meth)acrylic acid as defined above (preferably 2-hydroxyethyl(meth)acrylate) or at least one hydroxylated amide of (meth)acrylic acid as defined above (preferably 2-hydroxyethyl (meth)acrylamide), preferably with at least one hydroxylated ester of (meth)acrylic acid, in quantities such that the OH/NCO molar ratio, noted (r2) is less than 1.00.

(r1) is the NCO/OH molar ratio corresponding to the number of isocyanate groups (NCO) divided by the number of hydroxyl groups (OH) carried by all the polyisocyanates and polyols present in the reaction medium of step E1).

When the NCO-terminated polyurethane is obtained during step E1) from a mixture of polyisocyanates or several polyisocyanates added successively, the calculation of the ratio (r1) takes into account on the one hand the NCO groups carried by the all the polyisocyanates present in the reaction medium of step E1), and on the other hand the OH groups carried by the polyols present in the reaction medium of step E1).

(r2) is the OH/NCO molar ratio corresponding to the number of hydroxyl groups (OH) divided by the number of isocyanate groups (NCO) carried respectively by all the hydroxyl compounds and the isocyanates (particularly with regard to polyurethane with terminals NCO and optionally the unreacted polyisocyanates at the end of step E1)) present in the reaction medium of step E2). It is defined so as to achieve the number of isocyanate functions and acrylic functions desired per mole of polymer.

The polyols used in step E1) can have a number average molar mass (Mn) ranging from 400 to 12000 g/mol, preferably from 1000 to 8000 g/mol, more preferably from 1000 to 4000 g/mol.

Preferably, their hydroxyl functionality (average number of hydroxyl groups per molecule) can range from 2 to 3, more preferably equal to 2.

The polyols which can be used are preferably chosen from polyether polyols, polyester polyols, polyene polyols, polycarbonate polyols, polymers with -OH endings and their mixtures, more preferably from polyether polyols, polyester polyols and their mixtures, even more preferably among polyether polyols.

Advantageously, the polyether polyols are chosen from polyoxyalkylene diols or polyoxyalkylene triols, the alkylene part, linear or branched, preferably comprises from 1 to 4 carbon atoms, more preferably from 2 to 3 carbon atoms.

In particular, the polyether polyols are chosen from polyoxypropylene diols or triols (also referred to as polypropylene glycol (PPG) diols or triols) having a number average molecular mass (Mn) ranging from 400 to 12,000 g/mol and their mixtures.

As an example, we can cite the polyoxypropylene diol “ACCLAIM®” by BAYER, and the polyoxypropylene triol “VORANOL® CP3355” by DOW.

Advantageously, the polyester polyols are chosen from aliphatic, aromatic, arylaliphatic polyester diols and triols and their mixtures.

In particular, the polyester diols or triols can be chosen from polyester polyols of natural origin derived from castor oil and polyester polyols resulting from polycondensation:
- one or more aliphatic (linear, branched or cyclic) or aromatic polyols such as for example monoethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, butenediol, 1,6-hexanediol, cyclohexane dimethanol, tricyclodecane dimethanol, neopentyl glycol, cyclohexane dimethanol, glycerol, trimethylolpropane, 1,2,6-hexanetriol, sucrose, glucose, sorbitol, pentaerythritol, mannitol, N-methyldiethanolamine, triethanolamine, a dimeric fatty alcohol, a trimer fatty alcohol and mixtures thereof, with
- one or more polycarboxylic acids or its ester or anhydride derivative such as 1,6-hexanedioic acid, dodecanedioic acid, azelaic acid, sebacic acid, 1,18-octadecanedioic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, a dimeric fatty acid, a trimer fatty acid and mixtures of these acids, an unsaturated anhydride such as for example maleic or phthalic anhydride, or a lactone such as for example caprolactone.

As an example of polyester polyols, we can for example cite the following products with a hydroxyl functionality equal to 2: estolide polyols resulting from the polycondensation of one or more hydroxy acids, such as ricinoleic acid, on a diol (such as such as POLYCIN® D-2000 by VERTELLUS), TONE® 0240 by UNION CARBIDE which is a polycaprolactone, DYNACOLL® 7360 by EVONIK which results from the condensation of adipic acid with hexanediol, DYNACOLL® 7250 by EVONIK which is a polyester polyol, KURARAY® P-6010 by KURARAY which is a polyester polyol.

Advantageously, the polyene polyols are chosen from homopolymers and copolymers of butadiene and/or isoprene comprising terminal hydroxyl groups. Polyene polyols can be fully or partially hydrogenated.

The term “ terminal hydroxyl groups ” of a polyene polyol means the hydroxyl groups located at the ends of the main chain of the polyene polyol.

As an example of polyene polyols, we can cite:
- butadiene diol homopolymers comprising terminal hydroxyl groups such as POLY BD® R45HT (Mn = 2800 g/mol) or KRASOL® (Mn = 2400 to 3100 g/mol) marketed by CRAY VALLEY,
- isoprene diol homopolymers comprising terminal hydroxyl groups, such as POLY IP ^TM (unsaturated, Mn = 2000 g/mol) or EPOL ^TM (saturated, Mn = 2600 g/mol) marketed by IDEMITSU KOSAN.

As an example of polycarbonate diols, we can cite:
- the “CONVERGE® POLYOL 212-20” marketed by NOVOMER with Mn equal to 2000 g/mol whose hydroxyl index is 56 mg KOH/g,
- “POLYOL C-2090 and C-3090” marketed by KURARAY with Mn of 2000 and 3000 g/mol respectively and hydroxyl index of 56 and 37 mg KOH/g.

Polymers with -OH endings can be obtained by polyaddition reaction between one or more polyols, and one or more polyisocyanates, in quantities of polyisocyanates and polyols leading to an NCO/OH molar ratio strictly less than 1.0. The reaction can be carried out in the presence of a catalyst. The polyols and polyisocyanates that can be used can be those typically used for the preparation of polyurethanes with -NCO endings, and preferably those described in the present application.

The polyisocyanates which can be used according to the invention in step E1) can be added sequentially or reacted in the form of a mixture.

Advantageously, the polyisocyanates which can be used are diisocyanates, in particular chosen from the group consisting of isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), heptane diisocyanate, octane diisocyanate, nonane diisocyanate, decane diisocyanate, undecane diisocyanate, dodecane diisocyanate, 4,4'-methylenebis(cyclohexylisocyanate) (4,4'-HMDI), norbornane diisocyanate, norbornene diisocyanate, 1,4-cyclohexane diisocyanate (CHDI) , methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, propylcyclohexane diisocyanate, methyldiethylcyclohexane diisocyanate, cyclohexane dimethylene diisocyanate, 1,5-diisocyanato-2-methylpentane (MPDI), 1,6-diisocyanato-2,4,4 -trimethylhexane, 1,6-diisocyanato-2,2,4-trimethylhexane (TMDI), 4-isocyanatomethyl-1,8-octane diisocyanate (TIN), (2,5)-bis(isocyanatomethyl)bicyclo[2.2 .1]heptane (2,5-NBDI), (2,6)-bis(isocyanatomethyl)bicyclo[2.2.1]heptane (2,6-NBDI), 1,3-bis(isocyanatomethyl)cyclohexane (1 ,3-H6-XDI), 1,4-bis(isocyanatomethyl)-cyclohexane (1,4-H6-XDI), xylylene diisocyanate (XDI) (in particular m-xylylene diisocyanate (m-XDI)) , toluene diisocyanate (in particular 2,4-toluene diisocyanate (2,4-TDI) and/or 2,6-toluene diisocyanate (2,6-TDI)), diphenylmethane diisocyanate (in particular 4,4 '-diphenylmethane diisocyanate (4,4'-MDI) and/or 2,4'-diphenylmethane diisocyanate (2,4'-MDI)), tetramethylxylylene diisocyanate (TMXDI) (in particular tetramethyl (meta)xylylene diisocyanate) , of an HDI allophanate having for example the following formula (Y):

in which :

- k is an integer ranging from 1 to 2,

- q is an integer ranging from 0 to 9, preferably 2 to 5,

- R ¹⁴ may represent a hydrocarbon chain, saturated or unsaturated, cyclic or acyclic, linear or branched, comprising from 1 to 20 carbon atoms, preferably from 1 to 12 carbon atoms, more preferably from 6 to 14 carbon atoms, And

- R ¹³ may represent a divalent alkylene group, linear or branched, having 2 to 4 carbon atoms, preferably a divalent propylene group,

oligomers of these diisocyanates and their mixtures.

Preferably, the allophanate of formula (Y) is such that k, q, R ^is1 and R ^is2 are chosen such that said allophanate comprises an NCO isocyanate group content ranging from 12 to 14% by weight relative to the weight of said allophanate .

Preferably, the polyisocyanate(s) of step E1) is(are) chosen from the group consisting of hexamethylene diisocyanate, toluene diisocyanate (in particular the 2,4-TDI isomer, the 2,6-TDI isomer or mixtures thereof), meta-xylylene diisocyanate, isophorone diisocyanate, HDI allophanates, HDI oligomers and mixtures thereof, in particular hexamethylene diisocyanate.

The reaction between said polyisocyanates and said polyols can be carried out at a reaction temperature T1 lower than 95°C, preferably ranging from 65°C to 80°C.

The polyaddition reaction of step E1) can be carried out in the presence or absence of at least one reaction catalyst. Said reaction catalyst can be any catalyst known to those skilled in the art for catalyzing the formation of polyurethane by reaction of at least one polyisocyanate with at least one polyol. A quantity of up to 0.3% by weight of catalyst relative to the weight of the reaction medium of step E1) can be used, in particular from 0.02% to 0.2% by weight.

The polyurethane obtained in step E1) has a % NCO by weight which can range from 0.4% to 30% relative to the total weight of said polyurethane, preferably from 2% to 20%, more preferably from 5% to 15%. %.

The % NCO by weight can be determined by any method known to those skilled in the art, in particular by using an automatic titrator.

The polyurethane obtained in step E1) preferably has a viscosity ranging from 5000 to 200000 mPa.s at 23°C, more preferably a viscosity ranging from 5000 to 100000 mPa.s.

According to a preferred embodiment, the polyurethane comprising at least two NCO terminal functions is obtained by polyaddition reaction E1):
- i) at least one diisocyanate chosen from the group consisting of hexamethylene diisocyanate, toluene diisocyanate, meta-xylylene diisocyanate, isophorone diisocyanate, HDI allophanates and their mixtures, in particular hexamethylene diisocyanate ;
- ii) with at least one polyether diol having a number average molecular mass (Mn) greater than or equal to 400 g/mol.

The reaction of step E2) can be carried out at a reaction temperature T2 below 95°C, preferably ranging from 65°C to 80°C, preferably under anhydrous conditions.

The hydroxylated ester of (meth)acrylic acid of formula (X) can be used either pure or in the form of a mixture of different hydroxylated esters of (meth)acrylic acid, the hydroxyl number average ranging advantageously from 56 to 483 mg KOH/g of said mixture.

The hydroxylated amide of (meth)acrylic acid of formula (XI) can be used either pure or in the form of a mixture of different hydroxylated amides of (meth)acrylic acid, the hydroxyl index average ranging advantageously from 56 to 487 mg KOH/g of said mixture.

Step E2) is advantageously carried out with at least one hydroxylated ester of (meth)acrylic acid of formula (X), preferably of formula (X-1), (X-2) or (X-3), more preferably of formula (X-1), even more preferably chosen from 2-hydroxyethyl(meth)acrylate and 2-hydroxypropyl(meth)acrylate, in particular 2-hydroxyethyl(meth)acrylate.

The reaction catalyst that can be used for steps E1) and E2) can be any catalyst known to those skilled in the art to catalyze the formation of polyurethane by reaction of at least one polyisocyanate, at least one polyol and at least a hydroxyalkyl (meth)acrylate or a hydroxyalkyl (meth)acrylamide.

Preferably, one or more catalysts chosen from catalysts presenting no or little risk of toxicity are used. In particular, the reaction catalyst(s) are chosen from the group consisting of:
- organometallic derivatives of bismuth, such as bismuth neodecanoate sold under the name “BORCHIKAT®315” by the company OM Group, bismuth carboxylate sold under the name “K-KAT® XC B221” by the company KING INDUSTRIES,
- organometallic derivatives of tin other than tin dibutyl dilaurate, such as for example tin dioctyl dilaurate (DOTL) as sold under the name “TIB® KAT 217” by the company “TIB Chemical”,
- organometallic derivatives of zinc, such as zinc carboxylate sold under the name “BORCHI KAT®22” by the company OM Group,
- organometallic derivatives of titanium, such as titanium tetrabutoxide Ti(OCH ₂ CH ₂ CH ₂ CH ₃ ) ₄ , titanium ethyl acetoacetate sold under the name “TYZOR® PITA” by the company DUPONT,
- organometallic derivatives of zirconium, such as zirconium chelate sold under the name “K-KAT® A209”, zirconium acetylacetonate (Zr(acac) ₄ ), and zirconium tetraethanolate Zr(OCH ₂ CH ₃ ) ₄ , and
- their mixtures.

A quantity of up to 0.3% by weight of catalysts relative to the total weight of the reaction medium of step E2) can be used, preferably from 0.02% to 0.3% by weight of catalysts relative to to the total weight of the reaction medium of step E2).

According to a preferred embodiment, the aforementioned polyurethane is obtained by a process comprising the following steps:

- E1) the preparation of a polyurethane comprising at least two NCO terminal functions by polyaddition reaction:
i) at least one diisocyanate chosen from the group consisting of hexamethylene diisocyanate, toluene diisocyanate, meta-xylylene diisocyanate, isophorone diisocyanate, HDI allophanates and their mixtures, in particular hexamethylene diisocyanate ,
ii) with at least one polyether diol having a number average molecular mass (Mn) greater than or equal to 400 g/mol,

- E2) the reaction of the product formed at the end of step E1) with at least 2-hydroxyethyl(meth)acrylate, in particular 2-hydroxyethylacrylate, in quantities such as the OH/NCO molar ratio (noted r2) is less than or equal to 1.00.

A polyurethane comprising at least one acrylic group and at least one preferred isocyanate group is for example CN9303 by SARTOMER.

Alternatively, the polymer comprising at least one acrylic group and at least one isocyanate group may be a polyacrylate, preferably a polymethacrylate. The monomers used to synthesize polyacrylate can be (meth)acrylic monomers such as (meth)acrylic acid, (meth)acrylamide, (meth)acrylonitrile and (meth)acrylate. For example, these monomers can be chosen from (meth)acrylic acid, alkyl(meth)acrylic monomers and mixtures thereof, the alkyl group preferably having from 1 to 12 carbon atoms. Thus, this polymer (already comprising an acrylate end) can have a group, such as a hydroxy group for example, capable of reacting with a (poly)isocyanate to form the polymer according to the invention.

Alternatively, the polymer may be a polyester. In this case, the polyester can be synthesized by polycondensation of one or more polyhydric alcohols preferably comprising from 2 to 15 carbon atoms with polycarboxylic acids preferably comprising from 2 to 14 carbon atoms. Then, the resulting polyester polyols can be esterified in the presence of an unsaturated carboxylic acid monomer such as (meth)acrylic acid. In addition, one or more hydroxyl groups of the polyols can react with a polyisocyanate to form the polymer according to the invention.

The polymer comprising at least one acrylic group and at least one isocyanate group may comprise from 0.5 to 4 acrylic groups per polymer molecule, preferably from 1 to 2.5 acrylic groups per polymer molecule.

The polymer comprising at least one acrylic group and at least one isocyanate group may also comprise from 0.5 to 3 isocyanate groups per polymer molecule, preferably from 1 to 2.5 isocyanate groups per polymer molecule.

The isocyanate groups are distributed randomly at the end of the polymer chain. Certain individual molecules may possibly be devoid of acrylic group and/or isocyanate group.

The acrylic groups are distributed statistically at the end of the chain and/or in the middle of the chain of the polymer.

In addition, this polymer can have a viscosity of 5000 to 100000 mPa.s at 23°C. This viscosity can be measured with a Brookfield viscometer at 23°C.

The total content of polymer(s) comprising at least one acrylic group and at least one isocyanate group can range from 1% to 40% by weight, preferably from 1% to 25% by weight, more preferably from 2% to 15%. by weight, relative to the total weight of component B.

The polymer comprising at least one acrylic group and at least one isocyanate group can act both as a decomplexing agent to release the organoborane from the organoborane-amine complex (with its isocyanate group) and also as a radically polymerizable compound after its initiated polymerization. by organoborane (with the acrylic group). Thus, during crosslinking of the composition, a single homogeneous polymer network is advantageously created.

Acrylic monomer and/or polymer

Component A and/or component B further comprises at least one acrylic monomer and/or polymer, preferably at least one methacrylic monomer and/or polymer. The acrylic monomer and/or polymer is different from the polymer comprising at least one acrylic group and at least one isocyanate group in particular because it does not comprise an isocyanate group. The polymerization of this compound is carried out by the radical route, that is to say by a chain polymerization which involves radicals as the active species. Thus, the acrylic monomer and/or polymer can copolymerize with the polymer comprising at least one acrylic group and at least one isocyanate group.

The acrylic monomer and/or polymer may be chosen from acrylic acid, an acrylic ester, an acrylamide, an acrylonitrile, polymers thereof and mixtures thereof. It can also be chosen from alkylacrylic monomers and/or polymers and mixtures thereof, the alkyl group preferably having from 1 to 22 carbon atoms, preferably from 1 to 12 carbon atoms, and being linear, branched or cyclical. Preferably, the acrylic monomer and/or polymer is a methacrylic monomer and/or polymer, that is to say chosen from methacrylic acid, a methacrylic ester, a methacrylamide, a methacrylonitrile, the polymers of these and their mixtures. More preferably, the acrylic monomer and/or polymer is a (meth)acrylic ester or a mixture of (meth)acrylic esters with an acrylic ester polymer.

Advantageously, the acrylic monomer and/or polymer is chosen from alkyl and cycloalkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-(meth)acrylate. propyl, isopropyl (meth)acrylate, allyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-decyl (meth)acrylate, ( isodecyl meth)acrylate, n-dodecyl (meth)acrylate, tridecyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, C12-alkyl acrylate C14 (such as SR336 sold by SARTOMER), n-octadecyl acrylate, a C16-C18 alkyl acrylate (such as SR257C sold by SARTOMER), t-butyl cyclohexyl acrylate, acrylate of 3 ,3,5-trimethyl cyclohexyl and mixtures thereof, preferably from methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, Cyclohexyl (meth)acrylate, polymers thereof and mixtures thereof, in particular among methyl (meth)acrylate, cyclohexyl (meth)acrylate and their mixture.

By “(meth)acrylate” we mean an acrylate or a methacrylate.

In addition, the acrylic monomer and/or polymer can be chosen from (meth)acrylates comprising heteroatoms, that is to say acrylates and methacrylates which comprise at least one atom which is not a carbon or hydrogen in the group of the alcohol part of the ester (without taking into account the atoms of the ester group itself). Preferably, the heteroatom is oxygen. Thus, the acrylic monomer and/or polymer can be chosen from tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-ethoxypropyl (meth)acrylate, 3-ethoxypropyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, methoxy-polyethylene glycol (meth)acrylate (preferably comprising 2 to 8 repeating (ethoxy) units), ethylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate (preferably comprising 2 to 8 (ethoxy) repeating units), polypropylene glycol (meth)acrylate (preferably comprising 2 to 8 (propoxy) repeating units), (meth)acrylate (5-ethyl-1,3-dioxan-5-yl)methyl, a cyclic formal glycerol (meth)acrylate (such as VISIOMER ^® GLYFOMA marketed by EVONIK), polycaprolactone (meth)acrylate, mono-2 -(methacryloyloxy)ethyl succinate, 2-phenoxyethyl acrylate, 2-[2-[2-(2-phenoxyethoxy)ethoxy]ethoxy]ethyl acrylate, 2-[2-[2- (2-nonylphenoxyethoxy)ethoxy]ethoxy]ethyl, 2-[2-[2-(2-dodecyloxyethoxy)ethoxy]ethoxy]ethyl acrylate, polymers thereof and mixtures thereof, preferably from (meth )tetrahydrofurfuryl acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, mono-2-(methacryloyloxy)ethyl succinate , polymers thereof and mixtures thereof, in particular among tetrahydrofurfuryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, polymers of these and mixtures thereof, for example 2-(2-ethoxyethoxy)ethyl (meth)acrylate and/or a 2-hydroxyethyl (meth)acrylate polymer.

Diacrylates and dimethacrylates can also be used in the context of the invention. Such compounds include ethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1 ,6-hexanediol, 3-methyl-1,5-pentanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1 di(meth)acrylate, 10-decanediol, tricyclodecanedimethanol di(meth)acrylate, esterdiol diacrylate, alkoxylated aliphatic di(meth)acrylates such as diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, ethoxylated and/or propoxylated cyclohexanedimethanol di(meth)acrylate, di(meth)acrylate ethoxylated and/or propoxylated hexanediol, ethoxylated and/or propoxylated neopentyl glycol di(meth)acrylate, caprolactone modified hydroxypivalate neopentyl glycol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, di( polyethylene glycol meth)acrylate, propoxylated neopentyl glycol diacrylates and mixtures thereof.

Triacrylates and trimethacrylates can also be used in the context of the invention. Such compounds include glycerol tri(meth)acrylate, ethoxylated and/or propoxylated glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated and/or propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ethoxylated and/or propoxylated trimethylolpropane tri(meth)acrylate and mixtures thereof.

Compounds comprising more than three acrylate or methacrylate groups can also be used, such as pentaerythritol tetra(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, di-pentaerythritol penta(meth)acrylate, tetra( ethoxylated and/or propoxylated pentaerythritol meth)acrylates and mixtures thereof.

In addition, the acrylic monomer and/or polymer may be chosen from polymerizable (meth)acrylic polymers, obtained from one or more acrylic monomers as described above (in particular 2-hydroxyethyl (meth)acrylate). , such as (poly)urethanes (meth)acrylates, polyesters (meth)acrylates, polybutadiene (meth)acrylate and epoxy (meth)acrylates, preferably (poly)urethanes (meth)acrylates (in particular (poly) acrylate urethanes). Preferred compounds in this category are for example CN1963, CN1964, CN992, CN982, CN9002, CN9012, CN9200, CN964A85, CN965, CN966H90, CN991, CN9245S, CN998B80, CN9210, CN9276, , PRO21596, CN9014NS, CN9800, CN9400, CN9167, CN9170A86, CN9761, CN9165A marketed by the company SARTOMER, in particular CN966H90. The (poly)urethanes (meth)acrylates are preferably based on a polyester.

The acrylic monomer and/or polymer may also include one or more (meth)acrylamide monomers. These monomers can be chosen from (meth)acrylamide, N-(hydroxymethyl)acrylamide, N-(hydroxyethyl)acrylamide, N-(isobutoxymethyl)acrylamide, N-(3-methoxypropyl)acrylamide, N-[ tris(hydroxymethyl)methyl]acrylamide, N-isopropylacrylamide, N-[3-(dimethylamino)propyl]methacrylamide, diacetone acrylamide, N,N'-methylenedimethacrylamide, N,N'-methylenediacrylamide, N ,N'-(1,2-dihydroxyethylene)bismethacrylamide and N,N'-(1,2-dihydroxyethylene)bisacrylamide as well as among the (meth)acrylamides formed after reaction of (meth)acrylic acid (or chloride acyl of this acid) with primary and/or secondary amines such as 1,3-diaminopropane, N,N'-dimethyl-1,3-diaminopropane, 1,4-diaminobutane, polyamidoamines and polyoxyalkylenepolyamines .

According to a preferred embodiment, the acrylic monomer and/or polymer comprises at least one acrylic monomer chosen from methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) )2-ethylhexyl acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-(meth)acrylate -(2-ethoxyethoxy)ethyl, mono-2-(methacryloyloxy)ethyl succinate and their mixtures, preferably from methyl (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate and mixtures thereof. Preferably, the acrylic monomer is chosen from the methacrylates of this preferred embodiment and their mixtures, except 2-(2-ethoxyethoxy)ethyl (meth)acrylate which is preferably an acrylate.

The acrylic monomer(s) of this preferred embodiment can optionally be mixed with an acrylic polymer, preferably a (poly)urethane (meth)acrylate as described above.

When an acrylic polymer is used, the weight ratio of acrylic monomer(s)/acrylic polymer(s) is preferably between 0.15 and 0.5, more preferably between 0.15 and 0, 3, for example equal to 0.2.

The total content of acrylic monomer(s) and/or polymer(s) can range from 20% to 80% by weight, preferably from 30% to 75%, more preferably from 35% to 70% relative to the total weight of component A or B in which it is present.

According to a preferred embodiment, the at least acrylic monomer and/or polymer is in component B only. Thus, the above contents are preferably relative to the total weight of component B.

Decomplexing agent

Component B may further comprise a decomplexing agent, that is to say a compound (other than the polymer comprising at least one acrylic group and at least one isocyanate group) capable of reacting with the amine included in the organoborane complex. -amine, in order to release the organoborane.

This presence of a decomplexing agent is optional.

The decomplexing agent may be an isocyanate or one of its derivatives, a Lewis acid, a carboxylic acid, a mineral acid, a phosphonic acid, a sulfonic acid, an acyl chloride, an anhydride, an aldehyde, a compound 1, 3 dicarbonyl or an epoxy. Preferably, the decomplexing agent is an isocyanate or one of its derivatives.

By “isocyanate” is meant a compound comprising at least one, preferably at least two, isocyanate groups (polyisocyanate). Isocyanate derivatives include, for example, biurets, uretdiones, isocyanurates, allophanates and diisocyanate oligomers.

According to a preferred embodiment, the decomplexing agent is chosen from ethylene-1,2-diisocyanate, propylene-1,3-diisocyanate, butylene-1,4-diisocyanate, pentamethylene-1,5-diisocyanate (PDI), hexamethylene-1,6-diisocyanate (HDI), toluene-2,4 diisocyanate (2,4-TDI), toluene-2,6 diisocyanate (2,6-TDI), cyclopentylene- 1,3-diisocyanate, cyclohexylene-1,4-diisocyanate, cyclohexylene-1,2-diisocyanate, isophorone diisocyanate (IPDI), diphenylmethane-4,4'-diisocyanate (4,4'-MDI), diphenylmethane-2,4'-diisocyanate (2,4'-MDI), diphenylmethane-2,2'-diisocyanate (2,2'-MDI), diphenylpropane-4,4'-diisocyanate (DPDI), m-xylylene diisocyanate (m-XDI), tetramethylxylene diisocyanate (TMXDI), naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, m-phenylene diisocyanate (MPDI), p-phenylene diisocyanate ( PPDI), diphenylsulphone-4,4'-diisocyanate, furfurylene diisocyanate, 4,4',4"-triisocyanatotriphenylmethane, benzene 1,3,5-triisocyanate, HDI isocyanurate, TDI isocyanurate, m-XDI isocyanurate, IPDI isocyanurate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, HDI allophanate, HDI biuret, HDI uretdione, glycerol adduct /TDI, the TDI/trimethylolpropane adduct, the m-XDI/glycerol adduct, the m-XDI/trimethylolpropane adduct, the m-H6XDI/trimethylolpropane adduct, and mixtures thereof. Preferably, the decomplexing agent is chosen from ethylene-1,2-diisocyanate, propylene-1,3-diisocyanate, butylene-1,4-diisocyanate, PDI, HDI, IPDI, HDI isocyanurate, IPDI isocyanurate, HDI allophanate, HDI biuret, HDI uretdione and mixtures thereof, in particular HDI isocyanurate.

When the decomplexing agent is a Lewis acid, it can for example be chosen from tin chloride or titanium chloride.

When the decomplexing agent is a carboxylic acid, it can for example be chosen from formic acid, acetic acid, propanoic acid, ethyl-2-hexanoic acid, lauric acid, benzoic acid, and p-methoxybenzoic acid or among dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, maleic acid, adipic acid, acid phthalic acid, fumaric acid, glycolic acid, thioglycolic acid, lactic acid, isophthalic acid and terephthalic acid.

When the decomplexing agent is a mineral acid, it can for example be chosen from hydrochloric acid (HCl), sulfuric acid (H ₂ SO ₄ ), phosphoric acid (H ₃ PO ₄ ), phosphorous acid (H ₃ PO ₃ ), hypophosphorous acid (H ₃ PO ₂ ) and silicic acid.

When the decomplexing agent is a phosphonic acid, it can for example be chosen from vinylphosphonic acid, phenylphosphonic acid, methylphosphonic acid and octadecylphosphonic acid.

When the decomplexing agent is a sulfonic acid, it can for example be chosen from methanesulfonic acid and benzenesulfonic acid.

When the decomplexing agent is an anhydride, it can for example be chosen from acetic anhydride, propionic anhydride, acrylic anhydride, methacrylic anhydride, hexanoic anhydride, decanoic anhydride, lauric anhydride, benzoic anhydride, maleic anhydride, succinic anhydride, methyl succinic anhydride, 2-octen-1-yl succinic anhydride, 2-dodecen-1-yl succinic anhydride, dodecenylsuccinic anhydride, cyclohexanedicarboxylic anhydride, phthalic anhydride, trimellitic anhydride and pyromellitic anhydride.

When the decomplexing agent is an aldehyde, it can for example be chosen from benzaldehyde, o-, m- and p-nitrobenzaldehyde, 2,4-dichlorobenzaldehyde, p-tolylaldehyde and 3-methoxy-4- hydroxybenzaldehyde. Acetals and dialdehydes can also be used.

When the decomplexing agent is a 1,3 dicarbonyl compound, it can for example be chosen from methyl acetoacetate, ethyl acetoacetate, tert-butyl acetoacetate, 2-methacryloyloxyethyl acetoacetate , diethylene glycol bis-acetoacetate, polycaprolactone tris-acetoacetate, polypropylene glycol bis-acetoacetate, poly(styrene-co-allyl acetoacetate), N,N-dimethylacetoacetamide, N-methylacetoacetamide, acetoacetanilide , ethylene bis-acetoacetamide, polypropylene glycol bis-acetoacetamide and acetoacetamide.

The content of decomplexing agent can range from 0.1% to 50% by weight, preferably from 1% to 30% by weight, more preferably from 5% to 20% by weight, relative to the total weight of component B.

Charge

Advantageously, the two-component composition according to the invention further comprises one or more fillers, preferably mineral, in component A and/or B, preferably in component B.

According to one embodiment, the fillers can be chosen from talc, mica, kaolin, bentonite, aluminum oxides, titanium oxides, iron oxides, barium sulfate, hornblende, amphiboles , chrysotile, carbon black, carbon fibers, preferably hydrophobic fumed silica, molecular sieves, carbonate fillers, wollastonite, glass beads, glass fibers and mixtures thereof.

Advantageously, the filler(s) are chosen from carbon black, carbon nanostructures (in particular nanotubes), carbon fibers, preferably hydrophobic fumed silica, carbonate fillers, glass beads, glass fibers and their mixtures. Preferably, the filler(s) are chosen from carbon black, carbon nanostructures (in particular nanotubes), preferably hydrophobic fumed silica, carbonate fillers, glass beads and mixtures thereof.

Preferably, the fumed silica is hydrophobic, that is to say it has been treated with a hydrophobic compound, for example a silicone oil, preferably polydimethylsiloxane (PDMS).

Advantageously, the carbonated fillers are formed by the group consisting of alkali or alkaline earth metal carbonates and their mixtures, preferably the carbonated fillers are calcium carbonate or chalk, more preferably calcium carbonate, in particular carbonate of precipitated calcium covered with fatty acid salt (in particular fatty acid calcium).

The coating of the precipitated calcium carbonate may represent from 0.1% to 5% by weight, based on the total weight of the coated precipitated calcium carbonate.

Preferably, the fatty acid salt covering the precipitated calcium carbonate comprises or consists of more than 50% by weight, preferably 100% by weight, of a stearic acid salt, preferably calcium stearate. , relative to the total weight of fatty acid salts.

The total content of filler(s) can range from 1% to 50% by weight relative to the total weight of the component comprising (preferably B), preferably from 5% to 40% by weight, more preferably from 10% to 35% by weight.

Additional amine

Component A may also further comprise at least one additional amine, the additional amine being as defined above for the amine of the organoborane-amine complex.

The presence of the amine (in excess relative to the organoborane) makes it possible to avoid premature decomplexation of the organoborane, and thus to stabilize the organoborane-amine complex (and therefore part A of the composition) so as to increase its shelf life.

The additional amine may be the same or different from the amine present in the organoborane-amine complex. When it is different, it is preferably a polyetheramine or a polyimine (such as a polyethyleneimine).

The additional amine content can vary from 0.01% to 30% by weight, preferably from 0.01% to 25%, relative to the total weight of component A.

Other additives

The two-component composition according to the invention may also comprise in component A and/or B one or more additives chosen from plasticizers, tackifying resins, UV stabilizers, humidity absorbers, optical brighteners and rheological additives.

The total content of additives can range from 0.1% to 20% by weight relative to the total weight of the two-component composition, preferably from 1% to 10% by weight.

The plasticizer can be chosen from those known to those skilled in the art in the field of adhesives. For example, plasticizers based on phthalate (such as diisodecyl phthalate, diisononyl phthalate, etc.), polyol ester (such as pentaerythritol tetravalerate), alkylsulphonic acid esters (such as those identified by CAS: 70775-94-9), esters of 1,2-cyclohexane dicarboxylic acid (such as diisononyl hexahydrophthalate) and their mixtures, preferably esters of alkylsulphonic acids, in particular esters of alkylsulphonic and phenol acids.

The plasticizer content can range from 0.1% to 20% by weight relative to the total weight of the two-component composition, preferably from 1% to 10% by weight.

According to a preferred embodiment, component A may comprise one or more plasticizers. Preferably, the plasticizer content ranges from 5% to 40% by weight relative to the total weight of component A, preferably from 10% to 30% by weight.

The tackifying resin may in particular be chosen from: resins obtained by polymerization of terpene hydrocarbons and phenols, in the presence of Friedel-Crafts catalysts; resins obtained by a process comprising the polymerization of alpha-methyl styrene; rosins of natural origin or modified, and their hydrogenated, dimerized, polymerized or esterified derivatives with monoalcohols or polyols such as SYLVALITE® RE 100 resin which is an ester of rosin and pentaerethritol available from the company ARIZONA CHEMICAL; resins obtained by hydrogenation, polymerization or copolymerization of mixtures of unsaturated aliphatic hydrocarbons having approximately 5, 9 or 10 carbon atoms from petroleum cuts; terpene resins; copolymers based on natural terpenes; and acrylic resins having a viscosity at 100°C less than 100 Pa.s.

The UV stabilizers can be chosen from benzotriazoles, benzophenones, so-called hindered amines such as bis(2,2,6,6,-tetramethyl-4-piperidyl)sebaceate, and mixtures thereof.

The optical brightener may for example be 2,5-thiophenediylbis (5-tert-butyl-1,3-benzoxazole).

The rheological additives can be chosen from those known to those skilled in the art in the field of adhesives. For example, a micronized amide wax (such as CRAYVALLAC marketed by Arkema).

Advantageously, the two-component composition according to the invention does not include a solvent. By “solvent”, we mean in particular a solvent used in the field of adhesives and/or sealants.

The solvents are well known to those skilled in the art and include, for example, water, ethanol, isopropanol, ethyl acetate, butyl acetate, acetone, butanone, methyl isobutyl ketone, tetrahydrofuran, N,N-dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, acetonitrile, cyclohexane, benzene, toluene, xylene, etc.

In particular, the two-component composition according to the invention does not comprise N-methyl-2-pyrrolidone (NMP).

Other characteristics of the two-component composition according to the invention

Preferably, components A and B of the two-component composition according to the invention remain separate until said composition is used. Thus, the decomplexation of the organoborane and the initiation of polymerization begin when component A comes into contact with component B.

The volume ratio of component B to component A can range from 0.1 to 15, preferably from 1 to 12, for example equal to approximately 10.

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

- from 2% to 70% by weight of organoborane-amine complex in component A, relative to the total weight of component A,

- from 20% to 98% by weight of polymer polyol in component A, relative to the total weight of component A, the polymer polyol having a number average molar mass of less than 4500 g/mol,

- from 1% to 40% by weight of polymer(s) comprising at least one acrylic group and at least one isocyanate group in component B, relative to the total weight of component B,

- from 20% to 80% by weight of acrylic monomer(s) and/or polymer(s) relative to the total weight of component A or B in which it is present (preferably B),

- from 0.1% to 50% by weight of decomplexing agent in component B, relative to the total weight of component B,

- from 1% to 50% by weight of filler(s) relative to the total weight of the component comprising (preferably B), and

- optionally from 0.1% to 20% by weight of additives chosen from plasticizers, tackifying resins, UV stabilizers, humidity absorbers, optical brighteners and rheological additives, relative to the total weight of the composition two-component,

the volume ratio of component B to component A ranging from 0.1 to 15.

Preferably, the two-component composition according to the invention consists essentially of the ingredients mentioned above. By “essentially constituted”, it is meant that said composition comprises less than 5% by weight of ingredients other than the aforementioned ingredients, relative to the total weight of said composition, preferably less than 2% by weight, even more preferably less than 1% by weight.

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

According to a particular embodiment, the two-component composition according to the invention comprises:

- from 5% to 15% by weight of organoborane-amine complex in component A, relative to the total weight of component A, the organoborane-amine complex being preferably chosen from triethylborane-1,3-propanediamine, tri- n-butylborane-3-methoxypropylamine, triethylborane-diethylenetriamine, tri-n-butylborane-1,3-propanediamine, tri-sec-butylborane-1,3-propanediamine and triethylborane-1,6-hexanediamine,

- from 65% to 95% by weight of polymer polyol in component A, relative to the total weight of component A, the polymer polyol having a number average molar mass of less than 4500 g/mol and being preferably chosen from polyene polyols, polycarbonate polyester polyols and their mixtures, more preferably among polyene polyols,

- from 2% to 15% by weight of polymer(s) comprising at least one acrylic group and at least one isocyanate group in component B, relative to the total weight of component B, said polymer being a polyurethane preferably obtained by a process comprising the following steps:

E1) the preparation of a polyurethane comprising at least two NCO terminal functions by polyaddition reaction:
i) at least one diisocyanate chosen from the group consisting of hexamethylene diisocyanate, toluene diisocyanate, meta-xylylene diisocyanate, isophorone diisocyanate, HDI allophanates and their mixtures, in particular hexamethylene diisocyanate ,
ii) with at least one polyether diol having a number average molecular mass (Mn) greater than or equal to 400 g/mol,

E2) the reaction of the product formed at the end of step E1) with at least 2-hydroxyethyl(meth)acrylate, in particular 2-hydroxyethylacrylate, in quantities such as the OH/NCO molar ratio (noted r2 ) is less than or equal to 1.00,

- from 35% to 70% by weight of acrylic monomer(s) and/or polymer(s) in component B, relative to the total weight of component B, the monomer(s) and/or acrylic polymer(s) preferably comprising at least one acrylic monomer chosen from methyl (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2- (meth)acrylate (2-ethoxyethoxy)ethyl and their mixtures, optionally in mixture with an acrylic polymer, preferably a (poly)urethane (meth)acrylate,

- from 5% to 20% by weight of decomplexing agent in component B, relative to the total weight of component B, the decomplexing agent being preferably chosen from ethylene-1,2-diisocyanate, propylene-1 ,3-diisocyanate, butylene-1,4-diisocyanate, PDI, HDI, IPDI, HDI isocyanurate, IPDI isocyanurate, HDI allophanate, HDI biuret, uretdione of HDI and their mixtures,

- from 10% to 35% by weight of filler(s) in component B, relative to the total weight of component B, the filler(s) being preferably chosen from carbon black, carbon nanostructures, preferably hydrophobic fumed silica, carbonate fillers, glass beads and mixtures thereof, and

- optionally from 1% to 10% by weight of additives chosen from plasticizers, tackifying resins, UV stabilizers, humidity absorbers, optical brighteners and rheological additives, relative to the total weight of the two-component composition,

the volume ratio of component B to component A ranging from 1 to 12.

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

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

Other objects of the present invention

The present invention also relates to the use of the two-component composition according to the invention as an adhesive and/or binder. Thus, the two-component composition can be used to bond substrates together and/or to bind several ingredients. In particular, after coating the two-component composition on the surface of at least one substrate, the surface of an additional substrate can be brought into contact with the coated surface, so as to bond the two substrates.

Advantageously, at least one of the substrates is a substrate having a low surface energy. The other substrate may also be a substrate having a low surface energy or a material other than low surface energy substrates (in particular paper, a metal such as aluminum (optionally anodized), copper, zinc, brass, steel (in particular galvanized, stainless or electrogalvanized), a polymeric material such as polyamides, polyethers, polyurethanes, polyesters), preferably a substrate having a low surface energy or a metal.

By “substrate having a low surface energy”, we mean in particular a substrate having a surface energy less than or equal to 40 mJ/m ² , preferably less than or equal to 35 mJ/m ² . Substrates having a low surface energy are, for example, polyolefins and fluoropolymers such as polyethylene, polypropylene, polybutene, polyvinylidene fluoride, polyvinyl fluoride, polytetrafluoroethylene as well as their copolymers, in particular polypropylene and /or polyvinylidene fluoride. These surface energy values are well known in the state of the art.

According to one embodiment, the two-component composition according to the invention is used to bind the ingredients composing the anode and/or the cathode of a battery cell (for example, PVDF, metal oxide and electroconductive charge), preferably without using a solvent such as NMP, and/or for bonding the anode and/or the cathode to a metal collector (in particular copper or aluminum) of a battery cell.

The two-component composition according to the invention can also be used as a coating on the surface of a substrate. Thus, after crosslinking, the composition can form a layer covering the surface of the substrate in order, for example, to modify one or more properties of its surface. Preferably, this substrate has a low surface energy.

The two-component composition according to the invention can also be used as a primer, that is to say a layer coated on a substrate so as to improve one or more properties of the surface of this substrate (for example so as to improve the adhesion of the substrate with a material) so that one or more additional layers (including another adhesive composition) can be applied. Preferably, the substrate has a low surface energy.

Component A can be mixed with component B, in particular at a temperature of 15°C to 40°C, preferably 18°C to 25°C, before coating the two-component composition (mixture of components A and B) to the surface of a substrate. Then, the coating of the two-component composition can be carried out at a temperature of 15°C to 40°C, preferably 18°C to 25°C.

Alternatively, one of the components A or B of the composition can be coated on the surface of the substrate firstly then, in a second step, the other component can be coated on the surface of the substrate above the component already coating.

The coating of each of the components on the surface of the substrate can be carried out at a temperature of 15°C to 40°C, preferably 18°C to 25°C.

The present invention also relates to an article, in particular a battery cell, comprising the two-component composition according to the invention.

All the embodiments described above can be combined with each other. In particular, the different aforementioned ingredients of the two-component composition, and in particular the preferred modes, can be combined with each other.

The examples below are given purely to illustrate the invention and cannot be interpreted as limiting its scope.

Examples Example 1: Ingredients and measurement methods

Ingredients used

The following ingredients were used:

- Desmophen® C 1200 marketed by COVESTRO: linear aliphatic polycarbonate/polyester polyol having a molar mass of approximately 2000 g/mol;

- Krasol® LBH P 2000 marketed by Cray Valley: polybutadiene diol having an average molar mass in number Mn of approximately 2000 g/mol, polyene polyol;

- Krasol® LBH P 3000 marketed by Cray Valley: polybutadiene diol having an average molar mass in number Mn of approximately 3000 g/mol, polyene polyol;

- Krasol® LBH P 5000 marketed by Cray Valley: polybutadiene diol having a number average molar mass Mn of approximately 5000 g/mol, polyene polyol;

- Krasol® F 3000 marketed by Cray Valley: polyfarnesene diol having an average molar mass in Mn number of approximately 3000 g/mol, polyene polyol;

- Mesamoll® marketed by Lanxess: alkylsulfonic acid and phenol esters (CAS: 91082-17-6), plasticizer;

- TEB.DAP (triethylborane-1,3-diaminopropane) marketed by Ascensus specialties: CAS: 148861-07-8, organoborane-amine complex;

- CN9303 marketed by SARTOMER: polyurethane comprising acrylate groups and isocyanate groups;

- CN966H90 marketed by SARTOMER: urethane acrylate polymer based on a polyester mixed with 10% by weight of (2-(2-ethoxyethoxy)ethylacrylate) relative to the total weight of the mixture;

- Desmodur® Ultra N 3300 marketed by COVESTRO: hexamethylene isocyanurate diisocyanate, decomplexing agent;

- VISIOMER® c-HMA marketed by Evonik: cyclohexyl methacrylate (CAS: 101-43-9), methacrylate monomer;

- MMA (methyl methacrylate) marketed by Sigma-Aldrich: CAS: 80-62-6, methacrylate monomer;

- SR203H marketed by SARTOMER: tetrahydrofurfuryl methacrylate (CAS: 2455-24-5), methacrylate monomer;

- AEROSIL® R 202 marketed by Evonik: hydrophobic fumed silica (treated with a poly-dimethyl-siloxane), filler;

- CALOFORT® SV14 marketed by Specialty Minerals: precipitated calcium carbonate covered with calcium stearate, filler;

- “K&S” glass beads marketed by 3M: microspherical silica (SiO ₂ ), filler;

- rima plast Black 720 marketed by Grolman: dispersion comprising 20% by weight of carbon black in diisodecyl phthalate, relative to the total weight of the dispersion, pigment;

- C-NERGY Super C65 marketed by IMERYS: carbon black having an oil absorption index (OAN) of approximately 640 mL/100 g and a specific surface area (BET) of approximately 62 m ² /g, filler electrically conductive;

- ^VULCAN®

- Athlos SR1200 marketed by CABOT: carbon nanostructures (nanotubes) having a specific surface area (BET) of approximately 200 m ² /g, electroconductive charge.

Measurement methods

The shear strength was evaluated on plates with dimensions of 100 mm x 25 mm x 5 mm. The composition to be evaluated is applied between two plates on an area of 25 mm x 10 mm. The two plates are held against each other with clamps for 24 hours under standard conditions (approximately 23°C and 50% relative humidity), then sheared using a dynamometer at a speed of 10mm/min. The values obtained correspond to an average of 3 measurements. The shear strength is reported with the failure mode.

The shear strength on untreated polypropylene (PP) was evaluated on SIMONA® PP-DWU sheets. The shear strength on untreated polyvinylidene fluoride (PVDF) was evaluated on KYNAR 720 plates (ARKEMA). The shear strength between untreated polyvinylidene fluoride and metal was evaluated with KYNAR 720 (ARKEMA) plates for PVDF and E-Cu or SF-Cu plates for copper, alloy DX51 D+Z275 for galvanized steel. , E6 EV1 alloy 6060 for anodized aluminum and DC01 ZE 25/25 for electrogalvanized (electro-galvanized) steel.

The glass transition temperature (Tg) values were measured on an MCR302 rheometer (Anton Paar) by dynamic mechanical analysis (DMA) with bars of reticulated composition (24 hours after application) of the H2 test tube type (central part used, i.e. approximately 35*4*3 mm). After 5 min of stabilization, an oscillation equal to 1 Hz and a temperature ramp ranging from -50°C to 150°C (5°C/min) are applied, the values being recorded every 30 seconds.

Example 2: Effect of incorporating a polymer polyol

The different ingredients of each of components A and B are mixed in separate containers in the proportions indicated below, using a SpeedMixer ^TM mixer at room temperature (approximately 23°C). Component B is identical for the compositions in this example.

Component A for composition 0:

- 90.5% Mesamoll®, and

- 9.5% TEB.DAP,

the percentages being percentages by weight of the total weight of component A.

Component A for compositions 0bis, 1, 2, 3 and 4:

- 70% polyol,

- 20.5% Mesamoll®, and

- 9.5% TEB.DAP,

the percentages being percentages by weight of the total weight of component A.

Component B:

- 10% CN9303,

- 15% Desmodur® Ultra N 3300,

- 45% VISIOMER® c-HMA,

- 0.3% MMA,

- 9% AEROSIL® R 202,

- 19.3% CALOFORT® SV14,

- 0.7% rima plast Black 720, and

- 0.7% glass beads.

the percentages being percentages by weight of the total weight of component B.

Components A and B are then stored separately in a two-cartridge (protected from air and humidity) until use.

Each two-component composition 0 to 4 is obtained by mixing components A and B using a static mixer attached to the tip of the two-cartridge, at room temperature (23°C) in a ratio B/A in equal volume to 10. The polyol used in component A, as well as the properties of each two-component composition 0 to 4 (measured in accordance with Example 1) are indicated in Table 1. The shear resistance was evaluated between two plates of PP.

Composition 0 (comp.) 0bis (comp.) 1 (inv.) 2 (inv.) 3 (inv.) 4 (inv.) Polyol - Krasol® LBH P 5000 Krasol® LBH P 2000 Krasol® LBH P 3000 Desmophen® C 1200 Krasol® F 3000 Shear on PP (MPa) 3.2 5.7 4.2 5.5 3.8 4.2 Breaking mode R.C. R.C. R.C. RC and RS R.C. R.C. Tg hard segment (°C) ND ND +66.6 +68.2 +91.3 +67.8 Tg soft segment (°C) ND ND < -60 < -60 no soft segment -80.3

RC= cohesive failure, RS= support failure, ND= not determined

The results show that the introduction of a polymer polyol according to the invention (compositions 1-4) makes it possible to improve the shear resistance compared to the reference composition not comprising a polymer polyol (composition 0). Compositions 1-4 according to the invention therefore have improved adhesive properties. In addition, composition 2 according to the invention leads to a partial rupture of the support, which shows superior adhesion.

Furthermore, unlike compositions 1 to 4 according to the invention which are homogeneous, the comparative composition 0bis using a polyol polymer having a number average molar mass Mn of approximately 5000 g/mol leads to a material which is heterogeneous in depth and on the surface, not allowing its use as an adhesive.

Furthermore, compositions 1, 2 and 4 according to the invention also have the advantage of being less brittle than composition 3 according to the invention during mechanical stresses at room temperature, because the Tg of their hard segments is lower .

Example 3: Effect of incorporating an acrylic polymer and increasing the polyol polymer content

The two-component compositions of Example 3 are prepared in a manner similar to Example 2. In this example, a urethane acrylate polymer was added in component B (CN966H90).

Component B is obtained by mixing the following ingredients:

- 5% CN9303,

- 10% Desmodur® Ultra N 3300,

- 10% CN966H90,

- 45% VISIOMER® c-HMA,

- 0.3% MMA,

- 9% AEROSIL® R 202,

- 19.3% CALOFORT® SV14,

- 0.7% rima plast Black 720, and

- 0.7% glass beads.

the percentages being percentages by weight of the total weight of component B.

Component A is obtained by mixing the ingredients indicated in the table below (the percentages being percentages by weight of the total weight of component A). Components A and B are mixed in a B/A ratio by volume equal to 10, and the properties of the resulting two-component compositions 5 to 10 (measured in accordance with Example 1) are reported in this same table. The shear strength was evaluated between two PP plates.

Composition 5 (inv.) 6 (inv.) 7 (inv.) 8 (inv.) 9 (inv.) 10 (inv.) Krasol® LBH P 2000 70% 90.5% - - - - Krasol® LBH P 3000 - - 70% 90.5% - - Krasol® F 3000 - - - - 70% 90.5% Mesamoll® 20.5% - 20.5% - 20.5% - TEB.DAP 9.5% 9.5% 9.5% 9.5% 9.5% 9.5% Shear on PP (MPa) 5.1 5.6 4.9 5.8 5.1 5.4 Breaking mode RC and RS RC and RS RC and RS RC and RS RC and RS RC and RS Tg hard segment (°C) +84.9 +86 +84 +86.8 +85.7 +87.4 Tg soft segment (°C) -80.7 -80.2 -79.8 -80.5 -81.5 -78.7

RC= cohesive failure, RS= support failure

All compositions 5 to 10 according to the invention lead to partial rupture of the support, which shows that the compositions comprising an acrylic polymer have good adhesion properties.

In addition, the shear strength of compositions 5 to 10 according to the invention is improved in comparison to that of comparative composition 0 (Example 2).

Example 4: Evaluation of adhesive properties between PVDF and different metals

The two-component composition 2 according to the invention was also used to evaluate the adhesion between an untreated polyvinylidene fluoride plate and a metal plate.

The shear strength is measured in accordance with Example 1 and is indicated below for the different metals tested:

- PVDF/copper: 1.9 MPa;

- PVDF/zinc: 5.3 MPa;

- PVDF/brass: 3.7 MPa;

- PVDF/galvanized steel: 5.9 MPa;

- PVDF/stainless steel: 6.0 MPa;

- PVDF/anodized aluminum: 5.2 MPa;

- PVDF/aluminum 6082: 6.1 MPa;

- PVDF/electrogalvanized steel: 5.2 MPa.

The results show good adhesion between PVDF and the different metals tested, allowing their use in a battery cell. In addition, when the shear strength is greater than 4 MPa, a rupture of the support was observed, demonstrating good adhesion properties of the two-component composition 2 according to the invention.

Example 5: Two-component electroconductive composition according to the invention

In order to evaluate the adhesive properties of the two-component composition according to the invention in a battery cell, electroconductive compositions were prepared by introducing electroconductive charges into component B.

The two-component compositions of Example 5 are prepared in a manner similar to Example 2. Component A is obtained by mixing the following ingredients:

- 70% Krasol® F 3000,

- 20.5% Mesamoll®, and

- 9.5% TEB.DAP,

the percentages being percentages by weight of the total weight of component A.

Component B is obtained by mixing the ingredients indicated in the table below (the percentages being percentages by weight of the total weight of component B). Components A and B are mixed in a B/A ratio by volume equal to 10, and the properties of the resulting two-component compositions 11 to 14 (measured in accordance with Example 1) are reported in this same table. The shear strength was evaluated between two PP plates or two PVDF plates.

Composition 11 (inv.) 12 (inv.) 13 (inv.) 14 (inv.) CN9303 10% 10% 10% 10% Desmodur® Ultra N 3300 15% 15% 15% 15% SR203H 63% - - - MMA - 63% 60% 63% C-NERGY Super C65 12% 12% - - VULCAN® XC72R - - 15% - Athlos SR1200 - - - 1% AEROSIL® R 202 - - - 11% Shear on PP (MPa) and failure mode 5.6
RC and RS 4.9
RC and RS 4.8
RC and RS 4.4
R.C. Shear on PVDF (MPa) and failure mode 5.5
RC and RS 4.9
RC and RS 4.9
RC and RS 6.3
RS

RC= cohesive failure, RS= support failure

The two-component electroconductive compositions 11 to 14 according to the invention have good shear resistance, whether on PP or PVDF. The incorporation of electroconductive charges is therefore not detrimental to their adhesive properties.

The best adhesion results on PVDF were obtained for composition 14 according to the invention, comprising a mixture of carbon nanostructures and hydrophobic fumed silica. Indeed, its shear resistance is the highest of all the compositions tested, and total failure of the support was observed.

Thus, the two-component composition according to the invention is suitable for application in a battery cell, without the need to use an NMP type solvent. As a result, it can be used to bond the components of a battery cell in a dry process (solvent-free).

Claims (13)

Two-component composition comprising:
- a component A comprising:
- an organoborane-amine complex, and
- a polymer polyol having a number average molar mass of less than 4500 g/mol; And
- a component B comprising:
- a polymer comprising at least one acrylic group and at least one isocyanate group;
the component A and/or the component B further comprising at least one acrylic monomer and/or polymer. Two-component composition according to claim 1, in which the organoborane-amine complex is chosen from triethylborane-1,3-propanediamine, tri-n-butylborane-3-methoxypropylamine, triethylborane-diethylenetriamine, tri-n-butylborane-1 ,3-propanediamine, tri-sec-butylborane-1,3-propanediamine and triethylborane-1,6-hexanediamine, in particular triethylborane-1,3-propanediamine. Two-component composition according to claim 1 or 2, in which the polymer polyol, preferably polymer diol, is chosen from polyether polyols, polyester polyols, polyolefin polyols, fluoropolymer polyols, polyene polyols, polycarbonate polyols, polyester polycarbonate polyols and their mixtures, preferably from polyene polyols, polycarbonate polyester polyols and their mixtures, more preferably from polyene polyols. Two-component composition according to any one of claims 1 to 3, in which the polymer comprising at least one acrylic group and at least one isocyanate group is a polyurethane, preferably obtained by reaction of a polyurethane comprising at least two terminal -NCO functions , and at least one compound chosen from a hydroxylated ester of (meth)acrylic acid and a hydroxylated amide of (meth)acrylic acid, preferably a hydroxylated ester of (meth)acrylic acid. Two-component composition according to claim 4, in which the polyurethane comprising at least one acrylic group and at least one isocyanate group is prepared by a process comprising the following steps:
- E1) the preparation of a polyurethane comprising at least two terminal NCO functions (preferably at the ends of the main chain) by a polyaddition reaction:
- i) at least one polyisocyanate, preferably chosen from diisocyanates, triisocyanates, diisocyanate oligomers and mixtures thereof,
- ii) with at least one polyol, preferably chosen from polyether polyols, polyester polyols, polyene polyols, polycarbonate polyols, poly(ether-carbonate) polyols, polymers with -OH endings and their mixtures,
in quantities such that the NCO/OH molar ratio is strictly greater than 1.0, preferably ranges from 1.60 to 1.90, and preferably ranges from 1.65 to 1.85; And
- E2) the reaction of the product formed at the end of step E1) with at least one hydroxylated ester of (meth)acrylic acid (preferably 2-hydroxyethyl(meth)acrylate) or at least one hydroxylated amide of (meth)acrylic acid (preferably 2-hydroxyethyl (meth)acrylamide), preferably with at least one hydroxylated ester of (meth)acrylic acid, in quantities such as the OH/NCO molar ratio, noted ( r2) is less than 1.00. Two-component composition according to any one of claims 1 to 5, in which the acrylic monomer and/or polymer comprises at least one acrylic monomer chosen from methyl (meth) acrylate, ethyl (meth) acrylate, (meth) )butyl acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate , 2-(2-ethoxyethoxy)ethyl (meth)acrylate, mono-2-(methacryloyloxy)ethyl succinate and mixtures thereof, preferably from methyl (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate and mixtures thereof. Two-component composition according to any one of claims 1 to 6, in which component B further comprises a decomplexing agent. Two-component composition according to claim 7, in which the decomplexing agent is an isocyanate or one of its derivatives, a Lewis acid, a carboxylic acid, a mineral acid, a phosphonic acid, a sulfonic acid, an acyl chloride, an anhydride , an aldehyde, a 1,3 dicarbonyl compound or an epoxide, preferably an isocyanate or one of its derivatives. Two-component composition according to any one of claims 1 to 8, further comprising one or more fillers, preferably mineral, in component A and/or B, preferably in component B. Use of the two-component composition according to any one of Claims 1 to 9, as an adhesive and/or binder, as a coating or as a primer. Use according to claim 10, wherein at least one substrate is a substrate having a low surface energy. Use according to claim 10 or 11, for bonding the ingredients making up the anode and/or the cathode of a battery cell, preferably without using a solvent such as NMP, and/or for bonding the the anode and/or the cathode to a metal collector of a battery cell. Article, in particular battery cell, comprising the two-component composition according to any one of claims 1 to 9.